Ions in solution: Density corrected density functional theory (DC-DFT)
Kim, Min-Cheol; Sim, Eunji; Burke, Kieron
2014-05-14
Standard density functional approximations often give questionable results for odd-electron radical complexes, with the error typically attributed to self-interaction. In density corrected density functional theory (DC-DFT), certain classes of density functional theory calculations are significantly improved by using densities more accurate than the self-consistent densities. We discuss how to identify such cases, and how DC-DFT applies more generally. To illustrate, we calculate potential energy surfaces of HO·Cl{sup −} and HO·H{sub 2}O complexes using various common approximate functionals, with and without this density correction. Commonly used approximations yield wrongly shaped surfaces and/or incorrect minima when calculated self consistently, while yielding almost identical shapes and minima when density corrected. This improvement is retained even in the presence of implicit solvent.
Escudero, Daniel E-mail: thiel@kofo.mpg.de; Thiel, Walter E-mail: thiel@kofo.mpg.de
2014-05-21
We report an assessment of the performance of density functional theory-based multireference configuration interaction (DFT/MRCI) calculations for a set of 3d- and 4d-transition metal (TM) complexes. The DFT/MRCI results are compared to published reference data from reliable high-level multi-configurational ab initio studies. The assessment covers the relative energies of different ground-state minima of the highly correlated CrF{sub 6} complex, the singlet and triplet electronically excited states of seven typical TM complexes (MnO{sub 4}{sup ?}, Cr(CO){sub 6}, [Fe(CN){sub 6}]{sup 4?}, four larger Fe and Ru complexes), and the corresponding electronic spectra (vertical excitation energies and oscillator strengths). It includes comparisons with results from different flavors of time-dependent DFT (TD-DFT) calculations using pure, hybrid, and long-range corrected functionals. The DFT/MRCI method is found to be superior to the tested TD-DFT approaches and is thus recommended for exploring the excited-state properties of TM complexes.
Krykunov, Mykhaylo; Seth, Mike; Ziegler, Tom
2014-05-14
We have applied the relaxed and self-consistent extension of constricted variational density functional theory (RSCF-CV-DFT) for the calculation of the lowest charge transfer transitions in the molecular complex X-TCNE between X = benzene and TCNE = tetracyanoethylene. Use was made of functionals with a fixed fraction (?) of Hartree-Fock exchange ranging from ? = 0 to ? = 0.5 as well as functionals with a long range correction (LC) that introduces Hartree-Fock exchange for longer inter-electronic distances. A detailed comparison and analysis is given for each functional between the performance of RSCF-CV-DFT and adiabatic time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation. It is shown that in this particular case, all functionals afford the same reasonable agreement with experiment for RSCF-CV-DFT whereas only the LC-functionals afford a fair agreement with experiment using TDDFT. We have in addition calculated the CT transition energy for X-TCNE with X = toluene, o-xylene, and naphthalene employing the same functionals as for X = benzene. It is shown that the calculated charge transfer excitation energies are in as good agreement with experiment as those obtained from highly optimized LC-functionals using adiabatic TDDFT. We finally discuss the relation between the optimization of length separation parameters and orbital relaxation in the RSCF-CV-DFT scheme.
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MiniDFT MiniDFT Description MiniDFT is a plane-wave density functional theory (DFT) mini-app for modeling materials. Given an set of atomic coordinates and pseudopotentials, MiniDFT computes self-consistent solutions of the Kohn-Sham equations using either the LDA or PBE exchange-correlation functionals. For each iteration of the self-consistent field cycle, the Fock matrix is constructed and then diagonalized. To build the Fock matrix, Fast Fourier Transforms are used to transform orbitals from
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MiniDFT MiniDFT Description MiniDFT is a plane-wave denstity functional theory (DFT) mini-app for modeling materials. Given an set of atomic coordinates and pseudopotentials, MiniDFT computes self-consistent solutions of the Kohn-Sham equations using either the LDA or PBE exchange-correlation functionals. For each iteration of the self-consistent field cycle, the Fock matrix is constructed and then diagonalized. To build the Fock matrix, Fast Fourier Transforms are used to tranform orbitals from
Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo
Shulenburger, L.; Desjarlais, M. P.; Mattsson, T. R.
2014-10-01
We present an improved first-principles description of melting under pressure based on thermodynamic integration comparing Density Functional Theory (DFT) and quantum Monte Carlo (QMC) treatments of the system. The method is applied to address the longstanding discrepancy between density functional theory (DFT) calculations and diamond anvil cell (DAC) experiments on the melting curve of xenon, a noble gas solid where van der Waals binding is challenging for traditional DFT methods. The calculations show excellent agreement with data below 20 GPa and that the high-pressure melt curve is well described by a Lindemann behavior up to at least 80 GPa, a finding in stark contrast to DAC data.
Periodic subsystem density-functional theory
Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide
2014-11-07
By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn–Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn–Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.
Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Shulenburger, L.; Desjarlais, M. P.; Mattsson, T. R.
2014-10-01
We present an improved first-principles description of melting under pressure based on thermodynamic integration comparing Density Functional Theory (DFT) and quantum Monte Carlo (QMC) treatments of the system. The method is applied to address the longstanding discrepancy between density functional theory (DFT) calculations and diamond anvil cell (DAC) experiments on the melting curve of xenon, a noble gas solid where van der Waals binding is challenging for traditional DFT methods. The calculations show excellent agreement with data below 20 GPa and that the high-pressure melt curve is well described by a Lindemann behavior up to at least 80 GPa, amore » finding in stark contrast to DAC data.« less
Progress at the interface of wave-function and density-functional theories
Gidopoulos, Nikitas I.
2011-04-15
The Kohn-Sham (KS) potential of density-functional theory (DFT) emerges as the minimizing effective potential in a variational scheme that does not involve fixing the unknown single-electron density. Using Rayleigh Schroedinger (RS) perturbation theory (PT), we construct ab initio approximations for the energy difference, the minimization of which determines the KS potential directly - thereby bypassing DFT's traditional algorithm to search for the density that minimizes the total energy. From second-order RS PT, we obtain variationally stable energy differences to be minimized, solving the severe problem of variational collapse of orbital-dependent exchange-correlation functionals based on second-order RS PT.
Yu, J. M.; Balbuena, P. B.; Budzien, J. L.; Leung, Kevin
2011-02-22
We applied static and dynamic hybrid functional density functional theory (DFT) calculations to study the interactions of one and two excess electrons with ethylene carbonate (EC) liquid and clusters. Optimal structures of (EC)_{n} and (EC)_{n}^{-} clusters devoid of Li_{+} ions, n = 16, were obtained. The excess electron was found to be localized on a single EC in all cases, and the EC dimeric radical anion exhibits a reduced barrier associated with the breaking of the ethylene carbonoxygen covalent bond compared to EC_{-}. In ab initio molecular dynamics (AIMD) simulations of EC_{-} solvated in liquid EC, large fluctuations in the carbonyl carbonoxygen bond lengths were observed. AIMD simulations of a two-electron attack on EC in EC liquid and on Li metal surfaces yielded products similar to those predicted using nonhybrid DFT functionals, except that CO release did not occur for all attempted initial configurations in the liquid state.
Electrical double layers and differential capacitance in molten salts from density functional theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Frischknecht, Amalie L.; Halligan, Deaglan O.; Parks, Michael L.
2014-08-05
Classical density functional theory (DFT) is used to calculate the structure of the electrical double layer and the differential capacitance of model molten salts. The DFT is shown to give good qualitative agreement with Monte Carlo simulations in the molten salt regime. The DFT is then applied to three common molten salts, KCl, LiCl, and LiKCl, modeled as charged hard spheres near a planar charged surface. The DFT predicts strong layering of the ions near the surface, with the oscillatory density profiles extending to larger distances for larger electrostatic interactions resulting from either lower temperature or lower dielectric constant. Inmore » conclusion, overall the differential capacitance is found to be bell-shaped, in agreement with recent theories and simulations for ionic liquids and molten salts, but contrary to the results of the classical Gouy-Chapman theory.« less
Density functional theory based generalized effective fragment potential method
Nguyen, Kiet A. E-mail: ruth.pachter@wpafb.af.mil; Pachter, Ruth E-mail: ruth.pachter@wpafb.af.mil; Day, Paul N.
2014-06-28
We present a generalized Kohn-Sham (KS) density functional theory (DFT) based effective fragment potential (EFP2-DFT) method for the treatment of solvent effects. Similar to the original Hartree-Fock (HF) based potential with fitted parameters for water (EFP1) and the generalized HF based potential (EFP2-HF), EFP2-DFT includes electrostatic, exchange-repulsion, polarization, and dispersion potentials, which are generated for a chosen DFT functional for a given isolated molecule. The method does not have fitted parameters, except for implicit parameters within a chosen functional and the dispersion correction to the potential. The electrostatic potential is modeled with a multipolar expansion at each atomic center and bond midpoint using Stone's distributed multipolar analysis. The exchange-repulsion potential between two fragments is composed of the overlap and kinetic energy integrals and the nondiagonal KS matrices in the localized molecular orbital basis. The polarization potential is derived from the static molecular polarizability. The dispersion potential includes the intermolecular D3 dispersion correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The potential generated from the CAMB3LYP functional has mean unsigned errors (MUEs) with respect to results from coupled cluster singles, doubles, and perturbative triples with a complete basis set limit (CCSD(T)/CBS) extrapolation, of 1.7, 2.2, 2.0, and 0.5 kcal/mol, for the S22, water-benzene clusters, water clusters, and n-alkane dimers benchmark sets, respectively. The corresponding EFP2-HF errors for the respective benchmarks are 2.41, 3.1, 1.8, and 2.5 kcal/mol. Thus, the new EFP2-DFT-D3 method with the CAMB3LYP functional provides comparable or improved results at lower computational cost and, therefore, extends the range of applicability of EFP2 to larger system sizes.
Uncertainty Quantification for Nuclear Density Functional Theory...
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Uncertainty Quantification for Nuclear Density Functional Theory and Information Content of New Measurements Citation Details In-Document Search This content will become publicly...
Zinc surface complexes on birnessite: A density functional theory study
Kwon, Kideok D.; Refson, Keith; Sposito, Garrison
2009-01-05
Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.
Sjostrom, Travis; Crockett, Scott
2015-09-02
The liquid regime equation of state of silicon dioxide SiO_{2} is calculated via quantum molecular dynamics in the density range of 5 to 15 g/cc and with temperatures from 0.5 to 100 eV, including the α-quartz and stishovite phase Hugoniot curves. Below 8 eV calculations are based on Kohn-Sham density functional theory (DFT), and above 8 eV a new orbital-free DFT formulation, presented here, based on matching Kohn-Sham DFT calculations is employed. Recent experimental shock data are found to be in very good agreement with the current results. Finally both experimental and simulation data are used in constructing a new liquid regime equation of state table for SiO_{2}.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Sjostrom, Travis; Crockett, Scott
2015-09-02
The liquid regime equation of state of silicon dioxide SiO2 is calculated via quantum molecular dynamics in the density range of 5 to 15 g/cc and with temperatures from 0.5 to 100 eV, including the α-quartz and stishovite phase Hugoniot curves. Below 8 eV calculations are based on Kohn-Sham density functional theory (DFT), and above 8 eV a new orbital-free DFT formulation, presented here, based on matching Kohn-Sham DFT calculations is employed. Recent experimental shock data are found to be in very good agreement with the current results. Finally both experimental and simulation data are used in constructing a newmore » liquid regime equation of state table for SiO2.« less
Greeley, J.; Norskov, J.; Center for Nanoscale Materials; Technical Univ. of Denmark
2009-03-26
A density functional theory (DFT) -based, combinatorial search for improved oxygen reduction reaction (ORR) catalysts is presented. A descriptor-based approach to estimate the ORR activity of binary surface alloys, wherein alloying occurs only in the surface layer, is described, and rigorous, potential-dependent computational tests of the stability of these alloys in aqueous, acidic environments are presented. These activity and stability criteria are applied to a database of DFT calculations on nearly 750 binary transition metal surface alloys; of these, many are predicted to be active for the ORR but, with few exceptions, they are found to be thermodynamically unstable in the acidic environments typical of low-temperature fuel cells. The results suggest that, absent other thermodynamic or kinetic mechanisms to stabilize the alloys, surface alloys are unlikely to serve as useful ORR catalysts over extended periods of operation.
Xu, Zhuo Gu, Bo; Mori, Michiyasu; Maekawa, Sadamichi; Ziman, Timothy
2015-05-07
We analyze the spin Hall effect in CuIr alloys in theory by the combined approach of the density functional theory (DFT) and Hartree-Fock (HF) approximation. The spin Hall angle (SHA) is obtained to be negative without the local correlation effects. After including the local correlation effects of the 5d orbitals of Ir impurities, the SHA becomes positive with realistic correlation parameters and consistent with experiment [Niimi et al., Phys. Rev. Lett. 106, 126601 (2011)]. Moreover, our analysis shows that the DFT?+?HF approach is a convenient and general method to study the influence of local correlation effects on the spin Hall effect.
Using DFT Methods to Study Activators in Optical Materials
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Du, Mao-Hua
2015-08-17
Density functional theory (DFT) calculations of various activators (ranging from transition metal ions, rare-earth ions, ns2 ions, to self-trapped and dopant-bound excitons) in phosphors and scintillators are reviewed. As a single-particle ground-state theory, DFT calculations cannot reproduce the experimentally observed optical spectra, which involve transitions between multi-electronic states. However, DFT calculations can generally provide sufficiently accurate structural relaxation and distinguish different hybridization strengths between an activator and its ligands in different host compounds. This is important because the activator-ligand interaction often governs the trends in luminescence properties in phosphors and scintillators, and can be used to search for new materials.more » DFT calculations of the electronic structure of the host compound and the positions of the activator levels relative to the host band edges in scintillators are also important for finding optimal host-activator combinations for high light yields and fast scintillation response. Mn4+ activated red phosphors, scintillators activated by Ce3+, Eu2+, Tl+, and excitons are shown as examples of using DFT calculations in phosphor and scintillator research.« less
Density functional theory for carbon dioxide crystal
Chang, Yiwen; Mi, Jianguo Zhong, Chongli
2014-05-28
We present a density functional approach to describe the solid?liquid phase transition, interfacial and crystal structure, and properties of polyatomic CO{sub 2}. Unlike previous phase field crystal model or density functional theory, which are derived from the second order direct correlation function, the present density functional approach is based on the fundamental measure theory for hard-sphere repulsion in solid. More importantly, the contributions of enthalpic interactions due to the dispersive attractions and of entropic interactions arising from the molecular architecture are integrated in the density functional model. Using the theoretical model, the predicted liquid and solid densities of CO{sub 2} at equilibrium triple point are in good agreement with the experimental values. Based on the structure of crystal-liquid interfaces in different planes, the corresponding interfacial tensions are predicted. Their respective accuracies need to be tested.
Demján, Tamás; Vörös, Márton; Palummo, Maurizia; Gali, Adam
2014-08-14
Diamondoids are small diamond nanoparticles (NPs) that are built up from diamond cages. Unlike usual semiconductor NPs, their atomic structure is exactly known, thus they are ideal test-beds for benchmarking quantum chemical calculations. Their usage in spintronics and bioimaging applications requires a detailed knowledge of their electronic structure and optical properties. In this paper, we apply density functional theory (DFT) based methods to understand the electronic and optical properties of a few selected pure and modified diamondoids for which accurate experimental data exist. In particular, we use many-body perturbation theory methods, in the G{sub 0}W{sub 0} and G{sub 0}W{sub 0}+BSE approximations, and time-dependent DFT in the adiabatic local density approximation. We find large quasiparticle gap corrections that can exceed thrice the DFT gap. The electron-hole binding energy can be as large as 4 eV but it is considerably smaller than the GW corrections and thus G{sub 0}W{sub 0}+BSE optical gaps are about 50% larger than the Kohn-Sham (KS) DFT gaps. We find significant differences between KS time-dependent DFT and GW+BSE optical spectra on the selected diamondoids. The calculated G{sub 0}W{sub 0} quasiparticle levels agree well with the corresponding experimental vertical ionization energies. We show that nuclei dynamics in the ionization process can be significant and its contribution may reach about 0.5 eV in the adiabatic ionization energies.
Density Functional Theory Approach to Nuclear Fission (Conference...
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Density Functional Theory Approach to Nuclear Fission Citation Details In-Document Search Title: Density Functional Theory Approach to Nuclear Fission Authors: Schunck, N Publication ...
Error Analysis in Nuclear Density Functional Theory (Journal...
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Error Analysis in Nuclear Density Functional Theory Citation Details In-Document Search Title: Error Analysis in Nuclear Density Functional Theory Authors: Schunck, N ; McDonnell,...
Error Analysis in Nuclear Density Functional Theory (Journal...
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Error Analysis in Nuclear Density Functional Theory Citation Details In-Document Search Title: Error Analysis in Nuclear Density Functional Theory You are accessing a document...
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
McNally, Joshua S.; Noll, Bruce; Orme, Christopher J.; Wilson, Aaron D.
2015-05-04
Here, a density functional theory (DFT) analysis has been performed to explore the impact of steric interactions on the function of switchable polarity solvents (SPS) and their implications on a quantitative structure-activity relationship (QSAR) model previously proposed for SPS. An x-ray crystal structure of the N,N-dimethylcyclohexylammonium bicarbonate (Hdmcha) salt has been solved as an asymmetric unit containing two cation/anion pairs, with a hydrogen bonding interaction observed between the bicarbonate anions, as well as between the cation and anion in each pair. DFT calculations provide an optimized structure of Hdmcha that closely resembles experimental data and reproduces the cation/anion interaction withmore » the inclusion of a dielectric field. Relaxed potential energy surface (PES) scans have been performed on Hdmcha-based computational model compounds, differing in the size of functional group bonded to the nitrogen center, to assess the steric impact of the group on the relative energy and structural properties of the compound. Results suggest that both the length and amount of branching associated with the substituent impact the energetic limitations on rotation of the group along the N-R bond and NC-R bond, and disrupt the energy minimized position of the hydrogen bonded bicarbonate group. The largest interaction resulted from functional groups that featured five bonds between the ammonium proton and a proton on a functional group with the freedom of rotation to form a pseudo-six membered ring which included both protons.« less
Reshak, A.H.; Khan, Saleem Ayaz
2013-11-15
Graphical abstract: - Highlights: FPLAPW method is used for calculating the electronic and optical properties of CdGa{sub 2}X{sub 4}. Electronic and optical properties were calculated using LDA, GGA, EVGGA and mBJ. Band gap conformed that CdGa{sub 2}X{sub 4} are semiconductors fit for UV and visible light. The ECD shows that change in the bond length and bond nature affect the band gap. The dielectric tensor components and its derivatives show considerable anisotropy. - Abstract: A density functional theory (DFT) based on full potential linear augmented plane wave (FPLAPW) was used for calculating the electronic structure, charge density and optical properties of CdGa{sub 2}X{sub 4} (X = S, Se) compounds. Local density approximation (LDA), generalized gradient approximation (GGA), Engle Vasko generalized gradient approximation (EVGGA) and recently modified BeckeJohnson (mBJ) were applied to calculate the band structure, total and partial density of states. The investigation of band structures and density of states of CdGa{sub 2}X{sub 4} (X = S, Se) elucidate that mBJ potential show close agreement to the experimental results. The mBJ potential was selected for further explanation of optical properties of CdGa{sub 2}X{sub 4} (X = S, Se). The study of electronic charge density contours shows that change in the bond lengths and bond nature affect the band gap of the compounds. The two non-zero dielectric tensor components and its derivatives show considerable anisotropy between the perpendicular and parallel components. The present work provide accurate information about the combination (hybridization) of orbital, formation of bands and dispersion of non-zero tensor components of CdGa{sub 2}X{sub 4} (X = S, Se)
Guided basin-hopping search of small boron clusters with density functional theory
Ng, Wei Chun; Yoon, Tiem Leong; Lim, Thong Leng
2015-04-24
The search for the ground state structures of Boron clusters has been a difficult computational task due to the unique metalloid nature of Boron atom. Previous research works had overcome the problem in the search of the Boron ground-state structures by adding symmetry constraints prior to the process of locating the local minima in the potential energy surface (PES) of the Boron clusters. In this work, we shown that, with the deployment of a novel computational approach that incorporates density functional theory (DFT) into a guided global optimization search algorithm based on basin-hopping, it is possible to directly locate the local minima of small Boron clusters in the PES at the DFT level. The ground-state structures search algorithm as proposed in this work is initiated randomly and needs not a priori symmetry constraint artificially imposed throughout the search process. Small sized Boron clusters so obtained compare well to the results obtained by similar calculations in the literature. The electronic properties of each structures obtained are calculated within the DFT framework.
Hybrid density functional theory description of N- and C-doping of NiO
Nolan, Michael; Long, Run; English, Niall J.; Mooney, Damian A.
2011-06-14
The large intrinsic bandgap of NiO hinders its potential application as a photocatalyst under visible-light irradiation. In this study, we have performed first-principles screened exchange hybrid density functional theory with the HSE06 functional calculations of N- and C-doped NiO to investigate the effect of doping on the electronic structure of NiO. C-doping at an oxygen site induces gap states due to the dopant, the positions of which suggest that the top of the valence band is made up primarily of C 2p-derived states with some Ni 3d contributions, and the lowest-energy empty state is in the middle of the gap. This leads to an effective bandgap of 1.7 eV, which is of potential interest for photocatalytic applications. N-doping induces comparatively little dopant-Ni 3d interactions, but results in similar positions of dopant-induced states, i.e., the top of the valence band is made up of dopant 2p states and the lowest unoccupied state is the empty gap state derived from the dopant, leading to bandgap narrowing. With the hybrid density functional theory (DFT) results available, we discuss issues with the DFT corrected for on-site Coulomb description of these systems.
Density Functional Theory Calculations of Mass Transport in UO2
Andersson, Anders D.; Dorado, Boris; Uberuaga, Blas P.; Stanek, Christopher R.
2012-06-26
In this talk we present results of density functional theory (DFT) calculations of U, O and fission gas diffusion in UO{sub 2}. These processes all impact nuclear fuel performance. For example, the formation and retention of fission gas bubbles induce fuel swelling, which leads to mechanical interaction with the clad thereby increasing the probability for clad breach. Alternatively, fission gas can be released from the fuel to the plenum, which increases the pressure on the clad walls and decreases the gap thermal conductivity. The evolution of fuel microstructure features is strongly coupled to diffusion of U vacancies. Since both U and fission gas transport rates vary strongly with the O stoichiometry, it is also important to understand O diffusion. In order to better understand bulk Xe behavior in UO{sub 2{+-}x} we first calculate the relevant activation energies using DFT techniques. By analyzing a combination of Xe solution thermodynamics, migration barriers and the interaction of dissolved Xe atoms with U, we demonstrate that Xe diffusion predominantly occurs via a vacancy-mediated mechanism. Since Xe transport is closely related to diffusion of U vacancies, we have also studied the activation energy for this process. In order to explain the low value of 2.4 eV found for U migration from independent damage experiments (not thermal equilibrium) the presence of vacancy clusters must be included in the analysis. Next we investigate species transport on the (111) UO{sub 2} surface, which is motivated by the formation of small voids partially filled with fission gas atoms (bubbles) in UO{sub 2} under irradiation. Surface diffusion could be the rate-limiting step for diffusion of such bubbles, which is an alternative mechanism for mass transport in these materials. As expected, the activation energy for surface diffusion is significantly lower than for bulk transport. These results are further discussed in terms of engineering-scale fission gas release models. Finally, oxidation of UO{sub 2} and the importance of cluster formation for understanding thermodynamic and kinetic properties of UO{sub 2+x} are investigated.
Mattsson, Thomas R.; Root, Seth; Mattsson, Ann E.; Shulenburger, Luke; Magyar, Rudolph J.; Flicker, Dawn G.
2014-11-11
We use Sandia's Z machine and magnetically accelerated flyer plates to shock compress liquid krypton to 850 GPa and compare with results from density-functional theory (DFT) based simulations using the AM05 functional. We also employ quantum Monte Carlo calculations to motivate the choice of AM05. We conclude that the DFT results are sensitive to the quality of the pseudopotential in terms of scattering properties at high energy/temperature. A new Kr projector augmented wave potential was constructed with improved scattering properties which resulted in excellent agreement with the experimental results to 850 GPa and temperatures above 10 eV (110 kK). In conclusion, we present comparisons of our data from the Z experiments and DFT calculations to current equation of state models of krypton to determine the best model for high energy-density applications.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Mattsson, Thomas R.; Root, Seth; Mattsson, Ann E.; Shulenburger, Luke; Magyar, Rudolph J.; Flicker, Dawn G.
2014-11-11
We use Sandia's Z machine and magnetically accelerated flyer plates to shock compress liquid krypton to 850 GPa and compare with results from density-functional theory (DFT) based simulations using the AM05 functional. We also employ quantum Monte Carlo calculations to motivate the choice of AM05. We conclude that the DFT results are sensitive to the quality of the pseudopotential in terms of scattering properties at high energy/temperature. A new Kr projector augmented wave potential was constructed with improved scattering properties which resulted in excellent agreement with the experimental results to 850 GPa and temperatures above 10 eV (110 kK). Inmore » conclusion, we present comparisons of our data from the Z experiments and DFT calculations to current equation of state models of krypton to determine the best model for high energy-density applications.« less
Nakata, Hiroya; RIKEN, Research Cluster for Innovation, Nakamura Lab, 2-1 Hirosawa, Wako, Saitama 351-0198 ; Fedorov, Dmitri G.; Yokojima, Satoshi; Tokyo University of Pharmacy and Life Sciences, 1423-1 Horinouchi, Hachioji-shi, Tokyo 192-0392 ; Kitaura, Kazuo; Sakurai, Minoru; Nakamura, Shinichiro
2014-04-14
We extended the fragment molecular orbital (FMO) method interfaced with density functional theory (DFT) into spin unrestricted formalism (UDFT) and developed energy gradients for the ground state and single point excited state energies based on time-dependent DFT. The accuracy of FMO is evaluated in comparison to the full calculations without fragmentation. Electronic excitations in solvated organic radicals and in the blue copper protein, plastocyanin (PDB code: 1BXV), are reported. The contributions of solvent molecules to the electronic excitations are analyzed in terms of the fragment polarization and quantum effects such as interfragment charge transfer.
Fragment approach to constrained density functional theory calculations using Daubechies wavelets
Ratcliff, Laura E.; Genovese, Luigi; Mohr, Stephan; Deutsch, Thierry
2015-06-21
In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.
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Institute for Materieals Science Lecture Series 'D'++: Going Beyond DFT via GW and Vertex Corrections Professor R. S. Markiewicz Northeastern University, Boston Date: Wednesday, February 17, 2016 Time: 2:00 - 3:00pm Location: MSL Auditorium (TA-03 - Bldg 1698 - Room A103) Abstract: A large variety of approaches have been implemented for extending DFT (density-functional theory) calculations of band structure to account for stronger calculations. In particular, GW calculations are used to
Zhang, Yachao
2014-12-07
A first-principles study of critical temperatures (T{sub c}) of spin crossover (SCO) materials requires accurate description of the strongly correlated 3d electrons as well as much computational effort. This task is still a challenge for the widely used local density or generalized gradient approximations (LDA/GGA) and hybrid functionals. One remedy, termed density functional theory plus U (DFT+U) approach, introduces a Hubbard U term to deal with the localized electrons at marginal computational cost, while treats the delocalized electrons with LDA/GGA. Here, we employ the DFT+U approach to investigate the T{sub c} of a pair of iron(II) SCO molecular crystals (α and β phase), where identical constituent molecules are packed in different ways. We first calculate the adiabatic high spin-low spin energy splitting ΔE{sub HL} and molecular vibrational frequencies in both spin states, then obtain the temperature dependent enthalpy and entropy changes (ΔH and ΔS), and finally extract T{sub c} by exploiting the ΔH/T − T and ΔS − T relationships. The results are in agreement with experiment. Analysis of geometries and electronic structures shows that the local ligand field in the α phase is slightly weakened by the H-bondings involving the ligand atoms and the specific crystal packing style. We find that this effect is largely responsible for the difference in T{sub c} of the two phases. This study shows the applicability of the DFT+U approach for predicting T{sub c} of SCO materials, and provides a clear insight into the subtle influence of the crystal packing effects on SCO behavior.
Farberow, Carrie A.; Dumesic, James A.; Mavrikakis, Manos
2014-10-03
Reaction pathways are explored for low temperature (e.g., 400 K) reduction of nitric oxide by hydrogen on Pt(111). First-principles electronic structure calculations based on periodic, self-consistent density functional theory(DFT-GGA, PW91) are employed to obtain thermodynamic and kinetic parameters for proposed reaction schemes on Pt(111). The surface of Pt(111) during NO reduction by H? at low temperatures is predicted to operate at a high NO coverage, and this environment is explicitly taken into account in the DFT calculations. Maximum rate analyses are performed to assess the most likely reaction mechanisms leading to formation of N?O, the major product observed experimentally at low temperatures. The results of these analyses suggest that the reaction most likely proceeds via the addition of at least two H atoms to adsorbed NO, followed by cleavage of the N-O bond.
Thermally-assisted-occupation density functional theory with generalized-gradient approximations
Chai, Jeng-Da
2014-05-14
We extend the recently proposed thermally-assisted-occupation density functional theory (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)] to generalized-gradient approximation (GGA) exchange-correlation density functionals. Relative to our previous TAO-LDA (i.e., the local density approximation to TAO-DFT), the resulting TAO-GGAs are significantly superior for a wide range of applications, such as thermochemistry, kinetics, and reaction energies. For noncovalent interactions, TAO-GGAs with empirical dispersion corrections are shown to yield excellent performance. Due to their computational efficiency for systems with strong static correlation effects, TAO-LDA and TAO-GGAs are applied to study the electronic properties (e.g., the singlet-triplet energy gaps, vertical ionization potentials, vertical electron affinities, fundamental gaps, and symmetrized von Neumann entropy) of acenes with different number of linearly fused benzene rings (up to 100), which is very challenging for conventional electronic structure methods. The ground states of acenes are shown to be singlets for all the chain lengths studied here. With the increase of acene length, the singlet-triplet energy gaps, vertical ionization potentials, and fundamental gaps decrease monotonically, while the vertical electron affinities and symmetrized von Neumann entropy (i.e., a measure of polyradical character) increase monotonically.
Electronic transport properties of one dimensional lithium nanowire using density functional theory
Thakur, Anil; Kumar, Arun; Chandel, Surjeet; Ahluwalia, P. K.
2015-05-15
Single nanowire electrode devices are a unique platform for studying as energy storage devices. Lithium nanowire is of much importance in lithium ion batteries and therefore has received a great deal of attention in past few years. In this paper we investigated structural and electronic transport properties of Li nanowire using density functional theory (DFT) with SIESTA code. Electronic transport properties of Li nanowire are investigated theoretically. The calculations are performed in two steps: first an optimized geometry for Li nanowire is obtained using DFT calculations, and then the transport relations are obtained using NEGF approach. SIESTA and TranSIESTA simulation codes are used in the calculations correspondingly. The electrodes are chosen to be the same as the central region where transport is studied, eliminating current quantization effects due to contacts and focusing the electronic transport study to the intrinsic structure of the material. By varying chemical potential in the electrode regions, an I-V curve is traced which is in agreement with the predicted behavior. Agreement of bulk properties of Li with experimental values make the study of electronic and transport properties in lithium nanowires interesting because they are promising candidates as bridging pieces in nanoelectronics. Transmission coefficient and V-I characteristic of Li nano wire indicates that Li nanowire can be used as an electrode device.
Maeta, Takahiro; Sueoka, Koji
2014-08-21
Ge-based substrates are being developed for applications in advanced nano-electronic devices because of their higher intrinsic carrier mobility than Si. The stability and diffusion mechanism of impurity atoms in Ge are not well known in contrast to those of Si. Systematic studies of the stable sites of 2nd to 6th row element impurity atoms in Ge crystal were undertaken with density functional theory (DFT) and compared with those in Si crystal. It was found that most of the impurity atoms in Ge were stable at substitutional sites, while transition metals in Si were stable at interstitial sites and the other impurity atoms in Si were stable at substitutional sites. Furthermore, DFT calculations were carried out to clarify the mechanism responsible for the diffusion of impurity atoms in Ge crystals. The diffusion mechanism for 3d transition metals in Ge was found to be an interstitial-substitutional diffusion mechanism, while in Si this was an interstitial diffusion mechanism. The diffusion barriers in the proposed diffusion mechanisms in Ge and Si were quantitatively verified by comparing them to the experimental values in the literature.
Near surface stoichiometry in UO2: A density functional theory study
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Yu, Jianguo; Valderrama, Billy; Henderson, Hunter B.; Manuel, Michele V.; Allen, Todd
2015-08-01
The mechanisms of oxygen stoichiometry variation in UO2 at different temperature and oxygen partial pressure are important for understanding the dynamics of microstructure in these crystals. However, very limited experimental studies have been performed to understand the atomic structure of UO2 near surface and defect effects of near surface on stoichiometry in which the system can exchange atoms with the external reservoir. In this study, the near (110) surface relaxation and stoichiometry in UO2 have been studied with density functional theory (DFT) calculations. On the basis of the point-defect model (PDM), a general expression for the near surface stoichiometric variationmore » is derived by using DFT total-energy calculations and atomistic thermodynamics, in an attempt to pin down the mechanisms of oxygen exchange between the gas environment and defected UO2. By using the derived expression, it is observed that, under poor oxygen conditions, the stoichiometry of near surface is switched from hyperstoichiometric at 300 K with a depth around 3 nm to near-stoichiometric at 1000 K and hypostoichiometric at 2000 K. Furthermore, at very poor oxygen concentrations and high temperatures, our results also suggest that the bulk of the UO2 prefers to be hypostoichiometric, although the surface is near-stoichiometric.« less
Near surface stoichiometry in UO_{2}: A density functional theory study
Yu, Jianguo; Valderrama, Billy; Henderson, Hunter B.; Manuel, Michele V.; Allen, Todd
2015-08-01
The mechanisms of oxygen stoichiometry variation in UO_{2} at different temperature and oxygen partial pressure are important for understanding the dynamics of microstructure in these crystals. However, very limited experimental studies have been performed to understand the atomic structure of UO_{2} near surface and defect effects of near surface on stoichiometry in which the system can exchange atoms with the external reservoir. In this study, the near (110) surface relaxation and stoichiometry in UO_{2} have been studied with density functional theory (DFT) calculations. On the basis of the point-defect model (PDM), a general expression for the near surface stoichiometric variation is derived by using DFT total-energy calculations and atomistic thermodynamics, in an attempt to pin down the mechanisms of oxygen exchange between the gas environment and defected UO_{2}. By using the derived expression, it is observed that, under poor oxygen conditions, the stoichiometry of near surface is switched from hyperstoichiometric at 300 K with a depth around 3 nm to near-stoichiometric at 1000 K and hypostoichiometric at 2000 K. Furthermore, at very poor oxygen concentrations and high temperatures, our results also suggest that the bulk of the UO_{2} prefers to be hypostoichiometric, although the surface is near-stoichiometric.
Silvestrelli, Pier Luigi; Ambrosetti, Alberto
2014-03-28
The Density Functional Theory (DFT)/van der Waals-Quantum Harmonic Oscillator-Wannier function (vdW-QHO-WF) method, recently developed to include the vdW interactions in approximated DFT by combining the quantum harmonic oscillator model with the maximally localized Wannier function technique, is applied to the cases of atoms and small molecules (X=Ar, CO, H{sub 2}, H{sub 2}O) weakly interacting with benzene and with the ideal planar graphene surface. Comparison is also presented with the results obtained by other DFT vdW-corrected schemes, including PBE+D, vdW-DF, vdW-DF2, rVV10, and by the simpler Local Density Approximation (LDA) and semilocal generalized gradient approximation approaches. While for the X-benzene systems all the considered vdW-corrected schemes perform reasonably well, it turns out that an accurate description of the X-graphene interaction requires a proper treatment of many-body contributions and of short-range screening effects, as demonstrated by adopting an improved version of the DFT/vdW-QHO-WF method. We also comment on the widespread attitude of relying on LDA to get a rough description of weakly interacting systems.
Orbital-optimized density cumulant functional theory
Sokolov, Alexander Yu. Schaefer, Henry F.
2013-11-28
In density cumulant functional theory (DCFT) the electronic energy is evaluated from the one-particle density matrix and two-particle density cumulant, circumventing the computation of the wavefunction. To achieve this, the one-particle density matrix is decomposed exactly into the mean-field (idempotent) and correlation components. While the latter can be entirely derived from the density cumulant, the former must be obtained by choosing a specific set of orbitals. In the original DCFT formulation [W. Kutzelnigg, J. Chem. Phys. 125, 171101 (2006)] the orbitals were determined by diagonalizing the effective Fock operator, which introduces partial orbital relaxation. Here we present a new orbital-optimized formulation of DCFT where the energy is variationally minimized with respect to orbital rotations. This introduces important energy contributions and significantly improves the description of the dynamic correlation. In addition, it greatly simplifies the computation of analytic gradients, for which expressions are also presented. We offer a perturbative analysis of the new orbital stationarity conditions and benchmark their performance for a variety of chemical systems.
Self-consistent second-order Green's function perturbation theory...
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Self-consistent second-order Green's function perturbation theory for periodic systems ... Sponsoring Org: USDOE Country of Publication: United States Language: English Word Cloud ...
Joint Density-Functional Theory of Electrochemistry > Research...
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During the Chemical Transformation from Cobalt to Cobalt Phosphide Nanoparticles Joint Density-Functional Theory of Electrochemistry Double-band Electrode Channel Flow DEMS Cell...
Hexakis(4-phormylphenoxy)cyclotriphosphazene: X-ray and DFT-calculated structures
Albayrak, Cigdem Kosar, Basak; Odabasoglu, Mustafa; Bueyuekguengoer, Orhan
2010-12-15
The crystal structure of hexakis(4-phormylphenoxy)cyclotriphosphazene is determined by using X-ray diffraction and then the molecular structure is investigated with density functional theory (DFT). X-Ray study shows that the title compound has C-H-{pi} interaction with phosphazene ring. The molecules in the unit cell are packed with Van der Waals and dipole-dipole interactions and the molecules are packed in zigzag shaped. Optimized molecular geometry is calculated with DFT at B3LYP/6-311G(d,p) level. The results from both experimental and theoretical calculations are compared in this study.
Nazarian, Dalar; Ganesh, P.; Sholl, David S.
2015-09-30
We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionals for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.
Adsorption of silver dimer on graphene - A DFT study
Kaur, Gagandeep, E-mail: gaganj1981@yahoo.com [Department of Physics and Centre of Advanced Studies in Physics, Panjab University, Chandigarh-160014, India and Chandigarh Engineering College, Landran, Mohali-140307, Punjab (India); Gupta, Shuchi [Department of Physics and Centre of Advanced Studies in Physics, Panjab University, Chandigarh-160014, India and University Institute of Engineering and Technology, Panjab University, Chandigarh -160014 (India); Rani, Pooja; Dharamvir, Keya [Department of Physics and Centre of Advanced Studies in Physics, Panjab University, Chandigarh-160014 (India)
2014-04-24
We performed a systematic density functional theory (DFT) study of the adsorption of silver dimer (Ag{sub 2}) on graphene using SIESTA (Spanish Initiative for Electronic Simulations with Thousands of Atoms) package, in the generalized gradient approximation (GGA). The adsorption energy, geometry, and charge transfer of Ag2-graphene system are calculated. The minimum energy configuration for a silver dimer is parallel to the graphene sheet with its two atoms directly above the centre of carbon-carbon bond. The negligible charge transfer between the dimer and the surface is also indicative of a weak bond. The methodology demonstrated in this paper may be applied to larger silver clusters on graphene sheet.
Efficient Real-Time Time-Dependent Density Functional Theory...
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Efficient Real-Time Time-Dependent Density Functional Theory Method and its Application to a Collision of an Ion with a 2D Material Title: Efficient Real-Time Time-Dependent ...
Density functional theory study of skyrmion pinning by atomic...
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Journal Article: Density functional theory study of skyrmion pinning by atomic defects in MnSi Citation Details In-Document Search This content will become publicly available on ...
Preface: Special Topic on Advances in Density Functional Theory
Yang, Weitao
2014-05-14
This Special Topic Issue on the Advances in Density Functional Theory, published as a celebration of the fifty years of density functional theory, contains a retrospective article, a perspective article, and a collection of original research articles that showcase recent theoretical advances in the field. It provides a timely discussion reflecting a cross section of our understanding, and the theoretical and computational developments, which have significant implications in broad areas of sciences and engineering.
Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory
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(Journal Article) | SciTech Connect Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory Citation Details In-Document Search This content will become publicly available on April 11, 2017 Title: Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory Authors: Hinohara, Nobuo ; Nazarewicz, Witold Publication Date: 2016-04-11 OSTI Identifier: 1246764 Grant/Contract Number: SC0013365; SC0008511 Type: Publisher's Accepted Manuscript Journal Name: Physical Review
Density Functional Theory with Dissipation: Transport through Single Molecules
Kieron Burke
2012-04-30
A huge amount of fundamental research was performed on this grant. Most of it focussed on fundamental issues of electronic structure calculations of transport through single molecules, using density functional theory. Achievements were: (1) First density functional theory with dissipation; (2) Pseudopotential plane wave calculations with master equation; (3) Weak bias limit; (4) Long-chain conductance; and (5) Self-interaction effects in tunneling.
Mehmood, F.; Pachter, R.
2014-04-28
In this work, density functional theory (DFT) calculations have been used to investigate chemical sensing on surfaces of single-layer MoS{sub 2} and graphene, considering the adsorption of the chemical compounds triethylamine, acetone, tetrahydrofuran, methanol, 2,4,6-trinitrotoluene, o-nitrotoluene, o-dichlorobenzene, and 1,5-dicholoropentane. Physisorption of the adsorbates on free-standing surfaces was analyzed in detail for optimized material structures, considering various possible adsorption sites. Similar adsorption characteristics for the two surface types were demonstrated, where inclusion of a correction to the DFT functional for London dispersion was shown to be important to capture interactions at the interface of molecular adsorbate and surface. Charge transfer analyses for adsorbed free-standing surfaces generally demonstrated very small effects. However, charge transfer upon inclusion of the underlying SiO{sub 2} substrate rationalized experimental observations for some of the adsorbates considered. A larger intrinsic response for the electron-donor triethylamine adsorbed on MoS{sub 2} as compared to graphene was demonstrated, which may assist in devising chemical sensors for improved sensitivity.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Salerno, K. Michael; Frischknecht, Amalie L.; Stevens, Mark J.
2016-04-08
Here, negatively charged nanoparticles (NPs) in 1:1, 1:2, and 1:3 electrolyte solutions are studied in a primitive ion model using molecular dynamics (MD) simulations and classical density functional theory (DFT). We determine the conditions for attractive interactions between the like-charged NPs. Ion density profiles and NP–NP interaction free energies are compared between the two methods and are found to be in qualitative agreement. The NP interaction free energy is purely repulsive for monovalent counterions, but can be attractive for divalent and trivalent counterions. Using DFT, the NP interaction free energy for different NP diameters and charges is calculated. The depthmore » and location of the minimum in the interaction depend strongly on the NPs’ charge. For certain parameters, the depth of the attractive well can reach 8–10 kBT, indicating that kinetic arrest and aggregation of the NPs due to electrostatic interactions is possible. Rich behavior arises from the geometric constraints of counterion packing at the NP surface. Layering of counterions around the NPs is observed and, as secondary counterion layers form the minimum of the NP–NP interaction free energy shifts to larger separation, and the depth of the free energy minimum varies dramatically. We find that attractive interactions occur with and without NP overcharging.« less
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Liu, Jin; Adamska, Lyudmyla; Doorn, Stephen K.; Tretiak, Sergei
2015-05-14
Conformational structure and the electronic properties of various electronic excitations in cycloparaphenylenes (CPPs) are calculated using hybrid Density Functional Theory (DFT). The results demonstrate that wavefunctions of singlet and triplet excitons as well as the positive and negative polarons remain fully delocalized in CPPs. In contrast, these excitations in larger CPP molecules become localized on several phenyl rings, which are locally planarized, while the undeformed ground state geometry is preserved on the rest of the hoop. As evidenced by the measurements of bond-length alternation and dihedral angles, localized regions show stronger hybridization between neighboring bonds and thus enhanced electronic communication.more » This effect is even more significant in the smaller hoops, where phenyl rings have strong quinoid character in the ground state. Thus, upon excitation, electron–phonon coupling leads to the self-trapping of the electronic wavefunction and release of energy from fractions of an eV up to two eVs, depending on the type of excitation and the size of the hoop. The impact of such localization on electronic and optical properties of CPPs is systematically investigated and compared with the available experimental measurements.« less
Density functional theory and conductivity studies of boron-based anion receptors
Leung, Kevin; Chaudhari, Mangesh I.; Rempe, Susan B.; Fenton, Kyle R.; Pratt, III, Harry D.; Staiger, Chad L.; Nagasubramanian, Ganesan
2015-07-10
Anion receptors that bind strongly to fluoride anions in organic solvents can help dissolve the lithium fluoride discharge products of primary carbon monofluoride (CFx) batteries, thereby preventing the clogging of cathode surfaces and improving ion conductivity. The receptors are also potentially beneficial to rechargeable lithium ion and lithium air batteries. We apply Density Functional Theory (DFT) to show that an oxalate-based pentafluorophenyl-boron anion receptor binds as strongly, or more strongly, to fluoride anions than many phenyl-boron anion receptors proposed in the literature. Experimental data shows marked improvement in electrolyte conductivity when this oxalate anion receptor is present. The receptor is sufficiently electrophilic that organic solvent molecules compete with F^{–} for boron-site binding, and specific solvent effects must be considered when predicting its F^{–} affinity. To further illustrate the last point, we also perform computational studies on a geometrically constrained boron ester that exhibits much stronger gas-phase affinity for both F^{–} and organic solvent molecules. After accounting for specific solvent effects, however, its net F^{–} affinity is about the same as the simple oxalate-based anion receptor. Lastly, we propose that LiF dissolution in cyclic carbonate organic solvents, in the absence of anion receptors, is due mostly to the formation of ionic aggregates, not isolated F^{–} ions.
Liu, Jin; Adamska, Lyudmyla; Doorn, Stephen K.; Tretiak, Sergei
2015-05-14
Conformational structure and the electronic properties of various electronic excitations in cycloparaphenylenes (CPPs) are calculated using hybrid Density Functional Theory (DFT). The results demonstrate that wavefunctions of singlet and triplet excitons as well as the positive and negative polarons remain fully delocalized in CPPs. In contrast, these excitations in larger CPP molecules become localized on several phenyl rings, which are locally planarized, while the undeformed ground state geometry is preserved on the rest of the hoop. As evidenced by the measurements of bond-length alternation and dihedral angles, localized regions show stronger hybridization between neighboring bonds and thus enhanced electronic communication. This effect is even more significant in the smaller hoops, where phenyl rings have strong quinoid character in the ground state. Thus, upon excitation, electronphonon coupling leads to the self-trapping of the electronic wavefunction and release of energy from fractions of an eV up to two eVs, depending on the type of excitation and the size of the hoop. The impact of such localization on electronic and optical properties of CPPs is systematically investigated and compared with the available experimental measurements.
Density functional theory and conductivity studies of boron-based anion receptors
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Leung, Kevin; Chaudhari, Mangesh I.; Rempe, Susan B.; Fenton, Kyle R.; Pratt, III, Harry D.; Staiger, Chad L.; Nagasubramanian, Ganesan
2015-07-10
Anion receptors that bind strongly to fluoride anions in organic solvents can help dissolve the lithium fluoride discharge products of primary carbon monofluoride (CFx) batteries, thereby preventing the clogging of cathode surfaces and improving ion conductivity. The receptors are also potentially beneficial to rechargeable lithium ion and lithium air batteries. We apply Density Functional Theory (DFT) to show that an oxalate-based pentafluorophenyl-boron anion receptor binds as strongly, or more strongly, to fluoride anions than many phenyl-boron anion receptors proposed in the literature. Experimental data shows marked improvement in electrolyte conductivity when this oxalate anion receptor is present. The receptor ismore » sufficiently electrophilic that organic solvent molecules compete with F– for boron-site binding, and specific solvent effects must be considered when predicting its F– affinity. To further illustrate the last point, we also perform computational studies on a geometrically constrained boron ester that exhibits much stronger gas-phase affinity for both F– and organic solvent molecules. After accounting for specific solvent effects, however, its net F– affinity is about the same as the simple oxalate-based anion receptor. Lastly, we propose that LiF dissolution in cyclic carbonate organic solvents, in the absence of anion receptors, is due mostly to the formation of ionic aggregates, not isolated F– ions.« less
Weck, Philippe F.; Kim, Eunja; Jove-Colon, Carlos F.
2015-03-04
In this study, the structural, mechanical and thermodynamic properties of 1 : 1 layered dioctahedral kaolinite clay, with ideal Al_{2}Si_{2}O_{5}(OH)_{4} stoichiometry, were investigated using density functional theory corrected for dispersion interactions (DFT-D2). The bulk moduli of 56.2 and 56.0 GPa predicted at 298 K using the Vinet and BirchMurnaghan equations of state, respectively, are in good agreement with the recent experimental value of 59.7 GPa reported for well-crystallized samples. The isobaric heat capacity computed for uniaxial deformation of kaolinite along the stacking direction reproduces calorimetric data within 0.73.0% from room temperature up to its thermal stability limit.
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Weck, Philippe F.; Kim, Eunja; Jove-Colon, Carlos F.
2015-03-04
In this study, the structural, mechanical and thermodynamic properties of 1 : 1 layered dioctahedral kaolinite clay, with ideal Al2Si2O5(OH)4 stoichiometry, were investigated using density functional theory corrected for dispersion interactions (DFT-D2). The bulk moduli of 56.2 and 56.0 GPa predicted at 298 K using the Vinet and Birch–Murnaghan equations of state, respectively, are in good agreement with the recent experimental value of 59.7 GPa reported for well-crystallized samples. The isobaric heat capacity computed for uniaxial deformation of kaolinite along the stacking direction reproduces calorimetric data within 0.7–3.0% from room temperature up to its thermal stability limit.
Spin projection with double hybrid density functional theory
Thompson, Lee M.; Hratchian, Hrant P.
2014-07-21
A spin projected double-hybrid density functional theory is presented that accounts for different scaling of opposite and same spin terms in the second order correction. This method is applied to three dissociation reactions which in the unprojected formalism exhibit significant spin contamination with higher spin states. This gives rise to a distorted potential surface and can lead to poor geometries and energies. The projected method presented is shown to improve the description of the potential over unprojected double hybrid density functional theory. Comparison is made with the reference states of the two double hybrid functionals considered here (B2PLYP and mPW2PLYP) in which the projected potential surface is degraded by an imbalance in the description of dynamic and static correlation.
Multi-time wave functions for quantum field theory
Petrat, Sren; Tumulka, Roderich
2014-06-15
Multi-time wave functions such as ?(t{sub 1},x{sub 1},,t{sub N},x{sub N}) have one time variable t{sub j} for each particle. This type of wave function arises as a relativistic generalization of the wave function ?(t,x{sub 1},,x{sub N}) of non-relativistic quantum mechanics. We show here how a quantum field theory can be formulated in terms of multi-time wave functions. We mainly consider a particular quantum field theory that features particle creation and annihilation. Starting from the particleposition representation of state vectors in Fock space, we introduce multi-time wave functions with a variable number of time variables, set up multi-time evolution equations, and show that they are consistent. Moreover, we discuss the relation of the multi-time wave function to two other representations, the TomonagaSchwinger representation and the Heisenberg picture in terms of operator-valued fields on spacetime. In a certain sense and under natural assumptions, we find that all three representations are equivalent; yet, we point out that the multi-time formulation has several technical and conceptual advantages. -- Highlights: Multi-time wave functions are manifestly Lorentz-covariant objects. We develop consistent multi-time equations with interaction for quantum field theory. We discuss in detail a particular model with particle creation and annihilation. We show how multi-time wave functions are related to the TomonagaSchwinger approach. We show that they have a simple representation in terms of operator valued fields.
Differentiable but exact formulation of density-functional theory
Kvaal, Simen Ekstrm, Ulf; Helgaker, Trygve; Teale, Andrew M.; School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD
2014-05-14
The universal density functional F of density-functional theory is a complicated and ill-behaved function of the densityin particular, F is not differentiable, making many formal manipulations more complicated. While F has been well characterized in terms of convex analysis as forming a conjugate pair (E, F) with the ground-state energy E via the HohenbergKohn and Lieb variation principles, F is nondifferentiable and subdifferentiable only on a small (but dense) subset of its domain. In this article, we apply a tool from convex analysis, MoreauYosida regularization, to construct, for any ? > 0, pairs of conjugate functionals ({sup ?}E, {sup ?}F) that converge to (E, F) pointwise everywhere as ? ? 0{sup +}, and such that {sup ?}F is (Frchet) differentiable. For technical reasons, we limit our attention to molecular electronic systems in a finite but large box. It is noteworthy that no information is lost in the MoreauYosida regularization: the physical ground-state energy E(v) is exactly recoverable from the regularized ground-state energy {sup ?}E(v) in a simple way. All concepts and results pertaining to the original (E, F) pair have direct counterparts in results for ({sup ?}E, {sup ?}F). The MoreauYosida regularization therefore allows for an exact, differentiable formulation of density-functional theory. In particular, taking advantage of the differentiability of {sup ?}F, a rigorous formulation of KohnSham theory is presented that does not suffer from the noninteracting representability problem in standard KohnSham theory.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Nazarian, Dalar; Ganesh, P.; Sholl, David S.
2015-09-30
We compiled a test set of chemically and topologically diverse Metal–Organic Frameworks (MOFs) with high accuracy experimentally derived crystallographic structure data. The test set was used to benchmark the performance of Density Functional Theory (DFT) functionals (M06L, PBE, PW91, PBE-D2, PBE-D3, and vdW-DF2) for predicting lattice parameters, unit cell volume, bonded parameters and pore descriptors. On average PBE-D2, PBE-D3, and vdW-DF2 predict more accurate structures, but all functionals predicted pore diameters within 0.5 Å of the experimental diameter for every MOF in the test set. The test set was also used to assess the variance in performance of DFT functionalsmore » for elastic properties and atomic partial charges. The DFT predicted elastic properties such as minimum shear modulus and Young's modulus can differ by an average of 3 and 9 GPa for rigid MOFs such as those in the test set. Moreover, we calculated the partial charges by vdW-DF2 deviate the most from other functionals while there is no significant difference between the partial charges calculated by M06L, PBE, PW91, PBE-D2 and PBE-D3 for the MOFs in the test set. We find that while there are differences in the magnitude of the properties predicted by the various functionals, these discrepancies are small compared to the accuracy necessary for most practical applications.« less
Synergy between pair coupled cluster doubles and pair density functional theory
Garza, Alejandro J.; Bulik, Ireneusz W.; Henderson, Thomas M.; Scuseria, Gustavo E.
2015-01-28
Pair coupled cluster doubles (pCCD) has been recently studied as a method capable of accounting for static correlation with low polynomial cost. We present three combinations of pCCD with KohnSham functionals of the density and on-top pair density (the probability of finding two electrons on top of each other) to add dynamic correlation to pCCD without double counting. With a negligible increase in computational cost, these pCCD+DFT blends greatly improve upon pCCD in the description of typical problems where static and dynamic correlations are both important. We argue thatas a black-box method with low scaling, size-extensivity, size-consistency, and a simple quasidiagonal two-particle density matrixpCCD is an excellent match for pair density functionals in this type of fusion of multireference wavefunctions with DFT.
Descriptions of carbon isotopes within the energy density functional theory
Ismail, Atef; Cheong, Lee Yen; Yahya, Noorhana; Tammam, M.
2014-10-24
Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations.
Hole Localization in Molecular Crystals from Hybrid Density Functional Theory
Sai, Na; Barbara, Paul F.; Leung, Kevin
2011-06-02
We use first-principles computational methods to examine hole trapping in organic molecular crystals. We present a computational scheme based on the tuning of the fraction of exact exchange in hybrid density functional theory to eliminate the many-electron self-interaction error. With small organic molecules, we show that this scheme gives accurate descriptions of ionization and dimer dissociation. We demonstrate that the excess hole in perfect molecular crystals forms self-trapped molecular polarons. The predicted absolute ionization potentials of both localized and delocalized holes are consistent with experimental values.
Uncertainty Quantification and Propagation in Nuclear Density Functional
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Theory (Conference) | SciTech Connect Conference: Uncertainty Quantification and Propagation in Nuclear Density Functional Theory Citation Details In-Document Search Title: Uncertainty Quantification and Propagation in Nuclear Density Functional Theory Nuclear density functional theory (DFT) is one of the main theoretical tools used to study the properties of heavy and superheavy elements, or to describe the structure of nuclei far from stability. While on-going eff orts seek to better root
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Liu, Ping; An, Wei; Stacchiola, Dario; Xu, Fang
2015-10-16
Potassium (K) plays an essential role in promoting catalytic reaction in many established industrial catalytic processes. Here, we report a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) in understanding the effect of depositing K on the atomic and electronic structures as well as chemical activities of CuxO/Cu(111) (x≤2). The DFT calculations observe a pseudomorphic growth of K on CuxO/Cu(111) up to 0.19 monolayer (ML) of coverage, where K binds the surface via strong ionic interaction with chemisorbed oxygen and the relatively weak electrostatic interactions with copper ions, lower and upper oxygen on the CuxO rings.more » The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K displays great impact on the surface electronic structure of CuxO/Cu(111), which induces significant reduction in work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective. It varies depending on the nature of adsorbates. According to our results, K has little effect on surface acidity, while it enhances the surface basicity significantly. As a consequence, the presence of K does not help for CO adsorption on CuxO/Cu(111), but being able to accelerate the activation of CO2. Thus, such promotion strongly depends on the combinations from both geometric and electronic effects. Our results highlight the origin of promoting effect of alkalis in the design of catalysts for the complex reactions.« less
Zanatta, G.; Gottfried, C.; Silva, A. M.; Caetano, E. W. S.; Sales, F. A. M.; Freire, V. N.
2014-03-28
Results of optical absorption measurements are presented together with calculated structural, electronic, and optical properties for the anhydrous monoclinic L-asparagine crystal. Density functional theory (DFT) within the generalized gradient approximation (GGA) including dispersion effects (TS, Grimme) was employed to perform the calculations. The optical absorption measurements revealed that the anhydrous monoclinic L-asparagine crystal is a wide band gap material with 4.95 eV main gap energy. DFT-GGA+TS simulations, on the other hand, produced structural parameters in very good agreement with X-ray data. The lattice parameter differences ?a, ?b, ?c between theory and experiment were as small as 0.020, 0.051, and 0.022, respectively. The calculated band gap energy is smaller than the experimental data by about 15%, with a 4.23 eV indirect band gap corresponding to Z???? and Z???? transitions. Three other indirect band gaps of 4.30 eV, 4.32 eV, and 4.36 eV are assigned to ?3 ???, ?1 ???, and ?2 ??? transitions, respectively. ?-sol computations, on the other hand, predict a main band gap of 5.00 eV, just 50 meV above the experimental value. Electronic wavefunctions mainly originating from O 2pcarboxyl, C 2pside chain, and C 2pcarboxyl orbitals contribute most significantly to the highest valence and lowest conduction energy bands, respectively. By varying the lattice parameters from their converged equilibrium values, we show that the unit cell is less stiff along the b direction than for the a and c directions. Effective mass calculations suggest that hole transport behavior is more anisotropic than electron transport, but the mass values allow for some charge mobility except along a direction perpendicular to the molecular layers of L-asparagine which form the crystal, so anhydrous monoclinic L-asparagine crystals could behave as wide gap semiconductors. Finally, the calculations point to a high degree of optical anisotropy for the absorption and complex dielectric function, with more structured curves for incident light polarized along the 100 and 101 directions.
Sublinear scaling for time-dependent stochastic density functional theory
Gao, Yi; Neuhauser, Daniel; Baer, Roi; Rabani, Eran
2015-01-21
A stochastic approach to time-dependent density functional theory is developed for computing the absorption cross section and the random phase approximation (RPA) correlation energy. The core idea of the approach involves time-propagation of a small set of stochastic orbitals which are first projected on the occupied space and then propagated in time according to the time-dependent Kohn-Sham equations. The evolving electron density is exactly represented when the number of random orbitals is infinite, but even a small number (≈16) of such orbitals is enough to obtain meaningful results for absorption spectrum and the RPA correlation energy per electron. We implement the approach for silicon nanocrystals using real-space grids and find that the overall scaling of the algorithm is sublinear with computational time and memory.
The problem of the universal density functional and the density matrix functional theory
Bobrov, V. B. Trigger, S. A.
2013-04-15
The analysis in this paper shows that the Hohenberg-Kohn theorem is the constellation of two statements: (i) the mathematically rigorous Hohenberg-Kohn lemma, which demonstrates that the same ground-state density cannot correspond to two different potentials of an external field, and (ii) the hypothesis of the existence of the universal density functional. Based on the obtained explicit expression for the nonrel-ativistic particle energy in a local external field, we prove that the energy of the system of more than two non-interacting electrons cannot be a functional of the inhomogeneous density. This result is generalized to the system of interacting electrons. It means that the Hohenberg-Kohn lemma cannot provide justification of the universal density functional for fermions. At the same time, statements of the density functional theory remain valid when considering any number of noninteracting ground-state bosons due to the Bose condensation effect. In the framework of the density matrix functional theory, the hypothesis of the existence of the universal density matrix functional corresponds to the cases of noninteracting particles and to interaction in the Hartree-Fock approximation.
Self-interaction corrections in density functional theory
Tsuneda, Takao; Hirao, Kimihiko
2014-05-14
Self-interaction corrections for Kohn-Sham density functional theory are reviewed for their physical meanings, formulations, and applications. The self-interaction corrections get rid of the self-interaction error, which is the sum of the Coulomb and exchange self-interactions that remains because of the use of an approximate exchange functional. The most frequently used self-interaction correction is the Perdew-Zunger correction. However, this correction leads to instabilities in the electronic state calculations of molecules. To avoid these instabilities, several self-interaction corrections have been developed on the basis of the characteristic behaviors of self-interacting electrons, which have no two-electron interactions. These include the von Weizscker kinetic energy and long-range (far-from-nucleus) asymptotic correction. Applications of self-interaction corrections have shown that the self-interaction error has a serious effect on the states of core electrons, but it has a smaller than expected effect on valence electrons. This finding is supported by the fact that the distribution of self-interacting electrons indicates that they are near atomic nuclei rather than in chemical bonds.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Yamaoka, Hitoshi; Jarrige, Ignace; Schwier, Eike F.; Arita, Masashi; Shimada, Kenya; Tsujii, Naohito; Jiang, Jian; Hayashi, Hirokazu; Iwasawa, Hideaki; Namatame, Hirofumi; et al
2015-03-30
The electronic structure of Ce?Pd??X? (X = Si, Ge) has been studied using detailed density functional theory (DFT) calculations and high-resolution photoelectron spectroscopy (PES) measurements. The orbital decomposition of the electronic structure by DFT calculations indicates that Ce atoms at the (8c) site surrounded by 16 Pd atoms have a more localized nature and a tendency to be magnetic. Ce atoms in the (4a) site surrounded by 12 Pd and 6 X atoms, on the other, show only a negligible magnetic moment. In the photoemission valence-band spectra we observe a strong f? (Ce??) component with a small fraction of fmore(Ce?) component. The spectral weight of f component near the Fermi level Ce?Pd??Si? is stronger than that for Ce?Pd??Ge? at the 4d-4f resonance, suggesting stronger c-f hybridization in the former. This may hint to the origin of the large electronic specific coefficient of Ce?Pd??Si? compared to Ce?Pd??Ge?.less
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Yamaoka, Hitoshi; Schwier, Eike F.; Arita, Masashi; Shimada, Kenya; Tsujii, Naohito; Jarrige, Ignace; Jiang, Jian; Hayashi, Hirokazu; Iwasawa, Hideaki; Namatame, Hirofumi; et al
2015-03-30
The electronic structure of Ce₃Pd₂₀X₆ (X = Si, Ge) has been studied using detailed density functional theory (DFT) calculations and high-resolution photoelectron spectroscopy (PES) measurements. The orbital decomposition of the electronic structure by DFT calculations indicates that Ce atoms at the (8c) site surrounded by 16 Pd atoms have a more localized nature and a tendency to be magnetic. Ce atoms in the (4a) site surrounded by 12 Pd and 6 X atoms, on the other, show only a negligible magnetic moment. In the photoemission valence-band spectra we observe a strong f⁰ (Ce⁴⁺) component with a small fraction of f¹more » (Ce³⁺) component. The spectral weight of f¹ component near the Fermi level Ce₃Pd₂₀Si₆ is stronger than that for Ce₃Pd₂₀Ge₆ at the 4d-4f resonance, suggesting stronger c-f hybridization in the former. This may hint to the origin of the large electronic specific coefficient of Ce₃Pd₂₀Si₆ compared to Ce₃Pd₂₀Ge₆.« less
Ensemble density variational methods with self- and ghost-interaction-corrected functionals
Pastorczak, Ewa; Pernal, Katarzyna
2014-05-14
Ensemble density functional theory (DFT) offers a way of predicting excited-states energies of atomic and molecular systems without referring to a density response function. Despite a significant theoretical work, practical applications of the proposed approximations have been scarce and they do not allow for a fair judgement of the potential usefulness of ensemble DFT with available functionals. In the paper, we investigate two forms of ensemble density functionals formulated within ensemble DFT framework: the Gross, Oliveira, and Kohn (GOK) functional proposed by Gross et al. [Phys. Rev. A 37, 2809 (1988)] alongside the orbital-dependent eDFT form of the functional introduced by Nagy [J. Phys. B 34, 2363 (2001)] (the acronym eDFT proposed in analogy to eHF ensemble Hartree-Fock method). Local and semi-local ground-state density functionals are employed in both approaches. Approximate ensemble density functionals contain not only spurious self-interaction but also the so-called ghost-interaction which has no counterpart in the ground-state DFT. We propose how to correct the GOK functional for both kinds of interactions in approximations that go beyond the exact-exchange functional. Numerical applications lead to a conclusion that functionals free of the ghost-interaction by construction, i.e., eDFT, yield much more reliable results than approximate self- and ghost-interaction-corrected GOK functional. Additionally, local density functional corrected for self-interaction employed in the eDFT framework yields excitations energies of the accuracy comparable to that of the uncorrected semi-local eDFT functional.
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.
2015-04-02
The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K1 values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO22+ complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K1 values are significantly overestimated. Accurate predictions of the absolute log K1 values (root mean square deviation from experiment < 1.0 for log K1 values ranging from 0more » to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.« less
Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory
Vukovic, Sinisa; Hay, Benjamin P.; Bryantsev, Vyacheslav S.
2015-04-02
The ability to predict the equilibrium constants for the formation of 1:1 uranyl:ligand complexes (log K_{1 }values) provides the essential foundation for the rational design of ligands with enhanced uranyl affinity and selectivity. We also use density functional theory (B3LYP) and the IEFPCM continuum solvation model to compute aqueous stability constants for UO_{2}^{2+} complexes with 18 donor ligands. Theoretical calculations permit reasonably good estimates of relative binding strengths, while the absolute log K_{1} values are significantly overestimated. Accurate predictions of the absolute log K_{1} values (root mean square deviation from experiment < 1.0 for log K_{1} values ranging from 0 to 16.8) can be obtained by fitting the experimental data for two groups of mono and divalent negative oxygen donor ligands. The utility of correlations is demonstrated for amidoxime and imide dioxime ligands, providing a useful means of screening for new ligands with strong chelate capability to uranyl.
(E)-2-[(2-Bromophenylimino)methyl]-5-methoxyphenol: X-ray and DFT-calculated structures
Kosar, B. Albayrak, C.; Odabasoglu, M.; Bueyuekguengoer, O.
2010-12-15
The crystal structure of (E)-2-[(2-Bromophenylimino)methyl]-5-methoxyphenol is determined by using X-ray diffraction and then the molecular structure is investigated with density functional theory (DFT). X-Ray study shows that the title compound has a strong intramolecular O-H-N hydrogen bond and three dimensional crystal structure is primarily determined by C-H-{pi} and weak van der Waals interactions. The strong O-H-N bond is an evidence of the preference for the phenol-imine tautomeric form in the solid state. Optimized molecular geometry is calculated with DFT at the B3LYP/6-31G(d,p) level. The IR spectra of compound were recorded experimentally and calculated to compare with each other. The results from both experiment and theoretical calculations are compared in this study.
Modeling Excited States in TiO2 Nanoparticles: On the Accuracy of a TD-DFT Based Description
Berardo, Enrico; Hu, Hanshi; Shevlin, S. A.; Woodley, Scott M.; Kowalski, Karol; Zwijnenburg, Martijn A.
2014-03-11
We have investigated the suitability of Time-Dependent Density Functional Theory (TD-DFT) to describe vertical low-energy excitations in naked and hydrated titanium dioxide nanoparticles through a comparison with results from Equation-of-Motion Coupled Cluster (EOM-CC) quantum chemistry methods. We demonstrate that for most TiO2 nanoparticles TD-DFT calculations with commonly used exchange-correlation (XC-)potentials (e.g. B3LYP) and EOM-CC methods give qualitatively similar results. Importantly, however, we also show that for an important subset of structures, TD-DFT gives qualitatively different results depending upon the XC-potential used and that in this case only TD-CAM-B3LYP and TD-BHLYP calculations yield results that are consistent with those obtained using EOM-CC theory. Moreover, we demonstrate that the discrepancies for such structures arise from a particular combination of defects, excitations involving which are charge-transfer excitations and hence are poorly described by XC-potentials that contain no or low fractions of Hartree-Fock like exchange. Finally, we discuss that such defects are readily healed in the presence of ubiquitously present water and that as a result the description of vertical low-energy excitations for hydrated TiO2 nanoparticles is hence non-problematic.
Density Functional Theory in Surface Chemistry and Catalysis
Norskov, Jens
2011-05-19
Recent advances in the understanding of reactivity trends for chemistry at transition metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. Current status of the field is discussed with an emphasis on the role of coupling between theory and experiment and future challenges.
Magnetic and antimagnetic rotation in covariant density functional theory
Zhao, P. W.; Liang, H. Z.; Peng, J.; Ring, P.; Zhang, S. Q.; Meng, J.
2012-10-20
Progress on microscopic and self-consistent description of the magnetic rotation and antimagnetic rotation phenomena in tilted axis cranking relativistic mean-field theory based on a point-coupling interaction are briefly reviewed. In particular, the microscopic pictures of the shears mechanism in {sup 60}Ni and the two shears-like mechanism in {sup 105}Cd are discussed.
Lao, Ka Un; Herbert, John M.
2014-01-28
The performance of second-order symmetry-adapted perturbation theory (SAPT) calculations using Kohn-Sham (KS) orbitals is evaluated against benchmark results for intermolecular interactions. Unlike previous studies of this SAPT(KS) methodology, the present study uses non-empirically tuned long-range corrected (LRC) functionals for the monomers. The proper v{sub xc} (r)?0 asymptotic limit is achieved by tuning the range separation parameter in order to satisfy the condition that the highest occupied KS energy level equals minus the molecule's ionization energy, for each monomer unit. Tests for He{sub 2}, Ne{sub 2}, and the S22 and S66 data sets reveal that this condition is important for accurate prediction of the non-dispersion components of the energy, although errors in SAPT(KS) dispersion energies remain unacceptably large. In conjunction with an empirical dispersion potential, however, the SAPT(KS) method affords good results for S22 and S66, and also accurately predicts the whole potential energy curve for the sandwich isomer of the benzene dimer. Tuned LRC functionals represent an attractive alternative to other asymptotic corrections that have been employed in density-functional-based SAPT calculations, and we recommend the use of tuned LRC functionals in both coupled-perturbed SAPT(DFT) calculations and dispersion-corrected SAPT(KS) calculations.
Palladium dimers adsorbed on graphene: A DFT study
Kaur, Gagandeep; Gupta, Shuchi; Dharamvir, Keya
2015-05-15
The 2D structure of graphene shows a great promise for enhanced catalytic activity when adsorbed with palladium. We performed a systematic density functional theory (DFT) study of the adsorption of palladium dimer (Pd{sub 2}) on graphene using SIESTA package, in the generalized gradient approximation (GGA). The adsorption energy, geometry, and charge transfer of Pd{sub 2}-graphene system are calculated. Both horizontal and vertical orientations of Pd{sub 2} on graphene are studied. Our calculations revealed that the minimum energy configuration for Pd dimer is parallel to the graphene sheet with its two atoms occupying centre of adjacent hexagonal rings of graphene sheet. Magnetic moment is induced for Pd dimer adsorbed on graphene in vertical orientation while horizontal orientation of Pd dimer on graphene do not exhibit magnetism. Insignificant energy differences among adsorption sites means that dimer mobility on the graphene sheet is high. There is imperceptible distortion of graphene sheet perpendicular to its plane. However, some lateral displacements are seen.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Wang, Jianwei; Zhang, Yong; Wang, Lin-Wang
2015-07-31
We propose a systematic approach that can empirically correct three major errors typically found in a density functional theory (DFT) calculation within the local density approximation (LDA) simultaneously for a set of common cation binary semiconductors, such as III-V compounds, (Ga or In)X with X = N,P,As,Sb, and II-VI compounds, (Zn or Cd)X, with X = O,S,Se,Te. By correcting (1) the binary band gaps at high-symmetry points , L, X, (2) the separation of p-and d-orbital-derived valence bands, and (3) conduction band effective masses to experimental values and doing so simultaneously for common cation binaries, the resulting DFT-LDA-based quasi-first-principles methodmore » can be used to predict the electronic structure of complex materials involving multiple binaries with comparable accuracy but much less computational cost than a GW level theory. This approach provides an efficient way to evaluate the electronic structures and other material properties of complex systems, much needed for material discovery and design.« less
Liu, Ping; An, Wei; Stacchiola, Dario; Xu, Fang
2015-10-16
Potassium (K) plays an essential role in promoting catalytic reaction in many established industrial catalytic processes. Here, we report a combined study using scanning tunneling microscopy (STM) and density functional theory (DFT) in understanding the effect of depositing K on the atomic and electronic structures as well as chemical activities of Cu_{x}O/Cu(111) (x≤2). The DFT calculations observe a pseudomorphic growth of K on Cu_{x}O/Cu(111) up to 0.19 monolayer (ML) of coverage, where K binds the surface via strong ionic interaction with chemisorbed oxygen and the relatively weak electrostatic interactions with copper ions, lower and upper oxygen on the Cu_{x}O rings. The simulated STM pattern based on the DFT results agrees well with the experimental observations. The deposited K displays great impact on the surface electronic structure of Cu_{x}O/Cu(111), which induces significant reduction in work function and leads to a strong electron polarization on the surface. The promotion of K on the surface binding properties is selective. It varies depending on the nature of adsorbates. According to our results, K has little effect on surface acidity, while it enhances the surface basicity significantly. As a consequence, the presence of K does not help for CO adsorption on Cu_{x}O/Cu(111), but being able to accelerate the activation of CO_{2}. Thus, such promotion strongly depends on the combinations from both geometric and electronic effects. Our results highlight the origin of promoting effect of alkalis in the design of catalysts for the complex reactions.
Bethe Ansatz Approach to the Kondo Effect within Density-Functional Theory
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(Journal Article) | DOE PAGES Bethe Ansatz Approach to the Kondo Effect within Density-Functional Theory « Prev Next » Title: Bethe Ansatz Approach to the Kondo Effect within Density-Functional Theory Authors: Bergfield, Justin P. ; Liu, Zhen-Fei ; Burke, Kieron ; Stafford, Charles A. Publication Date: 2012-02-07 OSTI Identifier: 1099104 Type: Publisher's Accepted Manuscript Journal Name: Physical Review Letters Additional Journal Information: Journal Volume: 108; Journal Issue: 6; Journal
Density functional theory and conductivity studies of boron-based anion
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receptors (Journal Article) | SciTech Connect Journal Article: Density functional theory and conductivity studies of boron-based anion receptors Citation Details In-Document Search This content will become publicly available on July 10, 2016 Title: Density functional theory and conductivity studies of boron-based anion receptors Anion receptors that bind strongly to fluoride anions in organic solvents can help dissolve the lithium fluoride discharge products of primary carbon monofluoride
Mardis, Kristy L.; Webb, J.; Holloway, Tarita; Niklas, Jens; Poluektov, Oleg G.
2015-11-16
Organic photovoltaic (OPV) devices are a promising alternative energy source. Attempts to improve their performance have focused on the optimization of electron-donating polymers, while electron-accepting fullerenes have received less attention. Here, we report an electronic structure study of the widely used soluble fullerene derivatives PC61BM and PC71BM in their singly reduced state, that are generated in the polymer:fullerene blends upon light-induced charge separation. Density functional theory (DFT) calculations characterize the electronic structures of the fullerene radical anions through spin density distributions and magnetic resonance parameters. The good agreement of the calculated magnetic resonance parameters with those determined experimentally by advanced electron paramagnetic resonance (EPR) allows the validation of the DFT calculations. Thus, for the first time, the complete set of magnetic resonance parameters including directions of the principal g-tensor axes were determined. For both molecules, no spin density is present on the PCBM side chain, and the axis of the largest g-value lies along the PCBM molecular axis. While the spin density distribution is largely uniform for PC61BM, it is not evenly distributed for PC71BM.
Desnavi, Sameerah; Chakraborty, Brahmananda; Ramaniah, Lavanya M.
2014-04-24
The electronic structure and hydrogen storage capability of Yttrium-doped grapheme has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site of the hexagonal ring with a binding energy of 1.40 eV. Doping by Y makes the system metallic and magnetic with a magnetic moment of 2.11 ?{sub B}. Y decorated graphene can adsorb up to four hydrogen molecules with an average binding energy of 0.415 eV. All the hydrogen atoms are physisorbed with an average desorption temperature of 530.44 K. The Y atoms can be placed only in alternate hexagons, which imply a wt% of 6.17, close to the DoE criterion for hydrogen storage materials. Thus, this system is potential hydrogen storage medium with 100% recycling capability.
Gedanken densities and exact constraints in density functional theory
Perdew, John P.; Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122 ; Ruzsinszky, Adrienn; Sun, Jianwei; Burke, Kieron
2014-05-14
Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is not an approximation to it. We further derive a strongly and optimally tightened bound on the exchange enhancement factor of a two-electron density, which is satisfied by the local density approximation but is violated by all published GGA's or meta-GGA’s. Finally, some consequences of the non-uniform density-scaling behavior for the asymptotics of the exchange enhancement factor of a GGA or meta-GGA are given.
Isospin effects in N ≈ Z nuclei in extended density functional theory
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(Journal Article) | SciTech Connect Isospin effects in N ≈ Z nuclei in extended density functional theory Citation Details In-Document Search This content will become publicly available on January 25, 2017 Title: Isospin effects in N ≈ Z nuclei in extended density functional theory Authors: Satuła, Wojciech ; Nazarewicz, Witold Publication Date: 2016-01-25 OSTI Identifier: 1235743 Grant/Contract Number: DOE-DE-SC0008511; DOE-DE-SC0013365 Type: Publisher's Accepted Manuscript Journal
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Weck, Philippe F.; Kim, Eunja
2015-06-11
The structure, lattice dynamics and thermodynamic properties of bulk technetium were investigated within the framework of density functional theory. The phonon density of states spectrum computed with density functional perturbation theory closely matches inelastic coherent neutron scattering measurements. The thermal properties of technetium were derived from phonon frequencies calculated within the quasi-harmonic approximation (QHA), which introduces a volume dependence of phonon frequencies as a part of the anharmonic effect. As a result, the predicted thermal expansion and isobaric heat capacity of technetium are in excellent agreement with available experimental data for temperatures up to ~1600 K.
U?ur, Gkay; Candan, Abdullah
2014-10-06
First-principle calculations of structural, electronic, elastic and phonon properties of SnMg{sub 2}O{sub 4}, SnZn{sub 2}O{sub 4} and SnCd{sub 2}O{sub 4} compounds are presented, using the pseudo-potential plane waves approach based on density functional theory (DFT) within the generalized gradient approximation (GGA). The computed ground state structural parameters, i.e. lattice constants, internal free parameter and bulk modulus are in good agreement with the available theoretical results. Our calculated elastic constants are indicative of stability of SnX{sub 2}O{sub 4} (X=Mg, Zn, Cd) compounds in the spinel structure. The partial density of states (PDOS) of these compounds is in good agreement with the earlier ab-initio calculations. The phonon dispersion relations were calculated using the direct method. Phonon dispersion results indicate that SnZn{sub 2}O{sub 4} is dynamically stable, while SnMg{sub 2}O{sub 4} and SnCd{sub 2}O{sub 4} are unstable.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; Nenoff, Tina M.
2015-03-02
Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trendmore » in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.« less
Density functional theory for d- and f-electron materials and compounds
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Mattson, Ann E.; Wills, John M.
2016-02-12
Here, the fundamental requirements for a computationally tractable Density Functional Theory-based method for relativistic f- and (nonrelativistic) d-electron materials and compounds are presented. The need for basing the Kohn–Sham equations on the Dirac equation is discussed. The full Dirac scheme needs exchange-correlation functionals in terms of four-currents, but ordinary functionals, using charge density and spin-magnetization, can be used in an approximate Dirac treatment. The construction of a functional that includes the additional confinement physics needed for these materials is illustrated using the subsystem-functional scheme. If future studies show that a full Dirac, four-current based, exchange-correlation functional is needed, the subsystemmore » functional scheme is one of the few schemes that can still be used for constructing functional approximations.« less
Electronic Structure of Ligated CdSe Clusters: Dependence on DFT Methodology
Albert, VV; Ivanov, SA; Tretiak, S; Kilina, SV
2011-07-07
Simulations of ligated semiconductor quantum dots (QDs) and their physical properties, such as morphologies, QD-ligand interactions, electronic structures, and optical transitions, are expected to be very sensitive to computational methodology. We utilize Density Functional Theory (DFT) and systematically study how the choice of density functional, atom-localized basis set, and a solvent affects the physical properties of the Cd{sub 33}Se{sub 33} cluster ligated with a trimethyl phosphine oxide ligand. We have found that qualitative performance of all exchange-correlation (XC) functionals is relatively similar in predicting strong QD-ligand binding energy ({approx}1 eV). Additionally, all functionals predict shorter Cd-Se bond lengths on the QD surface than in its core, revealing the nature and degree of QD surface reconstruction. For proper modeling of geometries and QD-ligand interactions, however, augmentation of even a moderately sized basis set with polarization functions (e.g., LANL2DZ* and 6-31G*) is very important. A polar solvent has very significant implications for the ligand binding energy, decreasing it to 0.2-0.5 eV. However, the solvent model has a minor effect on the optoelectronic properties, resulting in persistent blue shifts up to {approx}0.3 eV of the low-energy optical transitions. For obtaining reasonable energy gaps and optical transition energies, hybrid XC functionals augmented by a long-range Hartree-Fock orbital exchange have to be applied.
Two-component hybrid time-dependent density functional theory within the Tamm-Dancoff approximation
Khn, Michael; Weigend, Florian
2015-01-21
We report the implementation of a two-component variant of time-dependent density functional theory (TDDFT) for hybrid functionals that accounts for spin-orbit effects within the Tamm-Dancoff approximation (TDA) for closed-shell systems. The influence of the admixture of Hartree-Fock exchange on excitation energies is investigated for several atoms and diatomic molecules by comparison to numbers for pure density functionals obtained previously [M. Khn and F. Weigend, J. Chem. Theory Comput. 9, 5341 (2013)]. It is further related to changes upon switching to the local density approximation or using the full TDDFT formalism instead of TDA. Efficiency is demonstrated for a comparably large system, Ir(ppy){sub 3} (61 atoms, 1501 basis functions, lowest 10 excited states), which is a prototype molecule for organic light-emitting diodes, due to its spin-forbidden triplet-singlet transition.
Neutron-star matter within the energy-density functional theory and neutron-star structure
Fantina, A. F.; Chamel, N.; Goriely, S.; Pearson, J. M.
2015-02-24
In this lecture, we will present some nucleonic equations of state of neutron-star matter calculated within the nuclear energy-density functional theory using generalized Skyrme functionals developed by the Brussels-Montreal collaboration. These equations of state provide a consistent description of all regions of a neutron star. The global structure of neutron stars predicted by these equations of state will be discussed in connection with recent astrophysical observations.
Hamiltonian Light-Front Ffield Theory in a Basis Function Approach
Vary, J.P.; Honkanen, H.; Li, Jun; Maris, P.; Brodsky, S.J.; Harindranath, A.; de Teramond, G.F.; Sternberg, P.; Ng, E.G.; Yang, C.
2009-05-15
Hamiltonian light-front quantum field theory constitutes a framework for the non-perturbative solution of invariant masses and correlated parton amplitudes of self-bound systems. By choosing the light-front gauge and adopting a basis function representation, we obtain a large, sparse, Hamiltonian matrix for mass eigenstates of gauge theories that is solvable by adapting the ab initio no-core methods of nuclear many-body theory. Full covariance is recovered in the continuum limit, the infinite matrix limit. There is considerable freedom in the choice of the orthonormal and complete set of basis functions with convenience and convergence rates providing key considerations. Here, we use a two-dimensional harmonic oscillator basis for transverse modes that corresponds with eigensolutions of the soft-wall AdS/QCD model obtained from light-front holography. We outline our approach, present illustrative features of some non-interacting systems in a cavity and discuss the computational challenges.
NO Chemisorption on Cu/SSZ-13: a Comparative Study from Infrared Spectroscopy and DFT Calculations
Zhang, Renqin; McEwen, Jean-Sabin; Kollar, Marton; Gao, Feng; Wang, Yilin; Szanyi, Janos; Peden, Charles HF
2014-11-07
The locations and energies of Cu ions in a Cu/SSZ-13 zeolite catalyst were investigated by density functional theory (DFT) calculations. For 'naked' Cu2+ ions (i.e., Cu2+ ions with no ligands in their coordination spheres other than zeolite lattice oxygen atoms), the more energetically favorable sites are within a 6-membered ring. However, with the presence of various adsorbates, the energy difference between 6- and 8-membered ring locations greatly diminishes. Specifically, Cu2+ ions are substantially stabilized by -OH ligands (as [CuII(OH)]+), making the extra-framework sites in an 8-membered ring energetically more favorable than 6-membered ring sites. Under fully dehydrated high vacuum conditions with different Si/Al and Cu/Al ratios, three chemisorbed NO species coexist upon exposure of NO to Cu/SSZ-13: NO+, Cu2+-NO and Cu+-NO. The relative signal intensities for these bands vary greatly with Si/Al ratios. The vibrational frequency of chemisorbed NO was found to be very sensitive to the location of Cu2+ ions. On the one hand, with the aid from DFT calculations, the nature for these vibrations can be assigned in detail. On the other hand, the relative intensities for various Cu2+-NO species provide a good measure of the nature of Cu2+ ions as functions of Si/Al and Cu/Al ratios and the presence of humidity. These new findings cast doubt on the generally accepted proposal that only Cu2+ ions located in 6-membered rings are catalytically active for NH3-SCR.
Ultra-nonlocality in density functional theory for photo-emission spectroscopy
Uimonen, A.-M.; Stefanucci, G.; INFN, Laboratori Nazionali di Frascati, Via E. Fermi 40, 00044 Frascati; European Theoretical Spectroscopy Facility , Louvain-la Neuve ; Leeuwen, R. van; European Theoretical Spectroscopy Facility , Louvain-la Neuve
2014-05-14
We derive an exact expression for the photocurrent of photo-emission spectroscopy using time-dependent current density functional theory (TDCDFT). This expression is given as an integral over the Kohn-Sham spectral function renormalized by effective potentials that depend on the exchange-correlation kernel of current density functional theory. We analyze in detail the physical content of this expression by making a connection between the density-functional expression and the diagrammatic expansion of the photocurrent within many-body perturbation theory. We further demonstrate that the density functional expression does not provide us with information on the kinetic energy distribution of the photo-electrons. Such information can, in principle, be obtained from TDCDFT by exactly modeling the experiment in which the photocurrent is split into energy contributions by means of an external electromagnetic field outside the sample, as is done in standard detectors. We find, however, that this procedure produces very nonlocal correlations between the exchange-correlation fields in the sample and the detector.
Ye, Jingyun; Liu, Changjun; Mei, Donghai; Ge, Qingfeng
2014-08-01
Methanol synthesis from CO2 hydrogenation on Pd4/In2O3 has been investigated using density functional theory (DFT) and microkinetic modeling. In this study, three possible routes in the reaction network of CO2 + H2 ? CH3OH + H2O have been examined. Our DFT results show that the HCOO route competes with the RWGS route whereas a high activation barrier kinetically blocks the HCOOH route. DFT results also suggest that H2COO* + H* ? H2CO* +OH* and cis-COOH* + H* ?CO* + H2O* are the rate limiting steps in the HCOO route and the RWGS route, respectively. Microkinetic modeling results demonstrate that the HCOO route is the dominant reaction route for methanol synthesis from CO2 hydrogenation. We found that the activation of H adatom on the small Pd cluster and the presence of H2O on the In2O3 substrate play important roles in promoting the methanol synthesis. The hydroxyl adsorbed at the interface of Pd4/In2O3 induces the transformation of the supported Pd4 cluster from a butterfly structure into a tetrahedron structure. This important structure change not only indicates the dynamical nature of the supported nanoparticle catalyst structure during the reaction but also shifts the final hydrogenation step from H2COH to CH3O.
Hao, Feng Mattsson, Ann E.; Armiento, Rickard
2014-05-14
We have previously proposed that further improved functionals for density functional theory can be constructed based on the Armiento-Mattsson subsystem functional scheme if, in addition to the uniform electron gas and surface models used in the Armiento-Mattsson 2005 functional, a model for the strongly confined electron gas is also added. However, of central importance for this scheme is an index that identifies regions in space where the correction provided by the confined electron gas should be applied. The electron localization function (ELF) is a well-known indicator of strongly localized electrons. We use a model of a confined electron gas based on the harmonic oscillator to show that regions with high ELF directly coincide with regions where common exchange energy functionals have large errors. This suggests that the harmonic oscillator model together with an index based on the ELF provides the crucial ingredients for future improved semi-local functionals. For a practical illustration of how the proposed scheme is intended to work for a physical system we discuss monoclinic cupric oxide, CuO. A thorough discussion of this system leads us to promote the cell geometry of CuO as a useful benchmark for future semi-local functionals. Very high ELF values are found in a shell around the O ions, and take its maximum value along the Cu–O directions. An estimate of the exchange functional error from the effect of electron confinement in these regions suggests a magnitude and sign that could account for the error in cell geometry.
Covariant density functional theory with two-phonon coupling in nuclei
Ring, P.; Litvinova, E.; Tselyaev, V.
2012-10-20
A full description of excited states within the framework of density functional theory requires energy dependent self energies. We present a new class of many-body models. It allows a parameter free description of the fragmentation of nuclear states induced by mode coupling of two-quasiparticle and two-phonon configurations. The method is applied for an investigation of low-lying dipole excitations in Sn isotopes with large neutron excess.
Fractional charge and spin errors in self-consistent Greens function theory
Phillips, Jordan J. Kananenka, Alexei A.; Zgid, Dominika
2015-05-21
We examine fractional charge and spin errors in self-consistent Greens function theory within a second-order approximation (GF2). For GF2, it is known that the summation of diagrams resulting from the self-consistent solution of the Dyson equation removes the divergences pathological to second-order Mller-Plesset (MP2) theory for strong correlations. In the language often used in density functional theory contexts, this means GF2 has a greatly reduced fractional spin error relative to MP2. The natural question then is what effect, if any, does the Dyson summation have on the fractional charge error in GF2? To this end, we generalize our previous implementation of GF2 to open-shell systems and analyze its fractional spin and charge errors. We find that like MP2, GF2 possesses only a very small fractional charge error, and consequently minimal many electron self-interaction error. This shows that GF2 improves on the critical failings of MP2, but without altering the positive features that make it desirable. Furthermore, we find that GF2 has both less fractional charge and fractional spin errors than typical hybrid density functionals as well as random phase approximation with exchange.
Double-hybrid density-functional theory with meta-generalized-gradient approximations
Souvi, Sidi M. O. Sharkas, Kamal; Toulouse, Julien; CNRS, UMR 7616, Laboratoire de Chimie Thorique, F-75005 Paris
2014-02-28
We extend the previously proposed one-parameter double-hybrid density-functional theory [K. Sharkas, J. Toulouse, and A. Savin, J. Chem. Phys. 134, 064113 (2011)] to meta-generalized-gradient-approximation (meta-GGA) exchange-correlation density functionals. We construct several variants of one-parameter double-hybrid approximations using the Tao-Perdew-Staroverov-Scuseria (TPSS) meta-GGA functional and test them on test sets of atomization energies and reaction barrier heights. The most accurate variant uses the uniform coordinate scaling of the density and of the kinetic energy density in the correlation functional, and improves over both standard Kohn-Sham TPSS and second-order Mller-Plesset calculations.
Time-dependent density functional theory quantum transport simulation in non-orthogonal basis
Kwok, Yan Ho; Xie, Hang; Yam, Chi Yung; Chen, Guan Hua; Zheng, Xiao
2013-12-14
Basing on the earlier works on the hierarchical equations of motion for quantum transport, we present in this paper a first principles scheme for time-dependent quantum transport by combining time-dependent density functional theory (TDDFT) and Keldysh's non-equilibrium Green's function formalism. This scheme is beyond the wide band limit approximation and is directly applicable to the case of non-orthogonal basis without the need of basis transformation. The overlap between the basis in the lead and the device region is treated properly by including it in the self-energy and it can be shown that this approach is equivalent to a lead-device orthogonalization. This scheme has been implemented at both TDDFT and density functional tight-binding level. Simulation results are presented to demonstrate our method and comparison with wide band limit approximation is made. Finally, the sparsity of the matrices and computational complexity of this method are analyzed.
Li, Li; Zhang, Guo; Chen, Lei; Bi, Hong-Mei; Shi, Ke-Ying
2013-02-15
Graphical abstract: The Ni(NiO)/semiconducting single-walled carbon nanotubes composite collected from the cathode after electro-deposition shows a high sensitivity to low-concentration NO gas at room temperature (18 C). Display Omitted Highlights: ? Ni(NiO) nanoparticles were deposited on semiconducting SWCNTs by electro-deposition. ? Ni(NiO)/semiconducting SWCNTs film shows a high sensitivity to NO gas at 18 C. ?Theoretical calculation reveals electron transfer from SWCNTs to NO via Ni. -- Abstract: Single-walled carbon nanotubes which contains metallic SWCNTs (m-SWCNTs) and semiconducting SWCNTs (s-SWCNTs) have been obtained under electric arc discharge. Their separation can be effectively achieved by the electro-deposition method. The Ni(NiO)/s-SWCNTs composite was found on cathode where Ni was partially oxidized to NiO at ambient condition with Ni(NiO) nanoparticles deposited uniformly on the bundles of SWCNTs. These results were confirmed by Raman spectra, transmission electron microscopy (TEM), scanning electron microscopy (SEM), UVvisNIR and TG characterizations. Furthermore, investigation of the gas sensing property of Ni(NiO)/s-SWCNTs composite film to NO gas at 18 C demonstrated the sensitivity was approximately 5% at the concentration of 97 ppb. Moreover, density functional theory (DFT) calculations were performed to explore the sensing mechanism which suggested the adsorption of NO molecules onto the composite through NNi interaction as well as the proposition of electron transfer mechanisms from SWCNTs to NO via the Ni medium.
Analytic cubic and quartic force fields using density-functional theory
Ringholm, Magnus; Gao, Bin; Thorvaldsen, Andreas J.; Ruud, Kenneth; Jonsson, Dan; High Performance Computing Group, University of TromsThe Arctic University of Norway, 9037 Troms ; Bast, Radovan; Ekstrm, Ulf; Helgaker, Trygve
2014-01-21
We present the first analytic implementation of cubic and quartic force constants at the level of KohnSham density-functional theory. The implementation is based on an open-ended formalism for the evaluation of energy derivatives in an atomic-orbital basis. The implementation relies on the availability of open-ended codes for evaluation of one- and two-electron integrals differentiated with respect to nuclear displacements as well as automatic differentiation of the exchangecorrelation kernels. We use generalized second-order vibrational perturbation theory to calculate the fundamental frequencies of methane, ethane, benzene, and aniline, comparing B3LYP, BLYP, and HartreeFock results. The HartreeFock anharmonic corrections agree well with the B3LYP corrections when calculated at the B3LYP geometry and from B3LYP normal coordinates, suggesting that the inclusion of electron correlation is not essential for the reliable calculation of cubic and quartic force constants.
Towards time-dependent current-density-functional theory in the non-linear regime
Escartn, J. M.; Vincendon, M.; Dinh, P. M.; Suraud, E.; Romaniello, P.; Reinhard, P.-G.
2015-02-28
Time-Dependent Density-Functional Theory (TDDFT) is a well-established theoretical approach to describe and understand irradiation processes in clusters and molecules. However, within the so-called adiabatic local density approximation (ALDA) to the exchange-correlation (xc) potential, TDDFT can show insufficiencies, particularly in violently dynamical processes. This is because within ALDA the xc potential is instantaneous and is a local functional of the density, which means that this approximation neglects memory effects and long-range effects. A way to go beyond ALDA is to use Time-Dependent Current-Density-Functional Theory (TDCDFT), in which the basic quantity is the current density rather than the density as in TDDFT. This has been shown to offer an adequate account of dissipation in the linear domain when the Vignale-Kohn (VK) functional is used. Here, we go beyond the linear regime and we explore this formulation in the time domain. In this case, the equations become very involved making the computation out of reach; we hence propose an approximation to the VK functional which allows us to calculate the dynamics in real time and at the same time to keep most of the physics described by the VK functional. We apply this formulation to the calculation of the time-dependent dipole moment of Ca, Mg and Na{sub 2}. Our results show trends similar to what was previously observed in model systems or within linear response. In the non-linear domain, our results show that relaxation times do not decrease with increasing deposited excitation energy, which sets some limitations to the practical use of TDCDFT in such a domain of excitations.
Wang, RuLin; Zheng, Xiao; Kwok, YanHo; Xie, Hang; Chen, GuanHua; Yam, ChiYung
2015-04-14
Understanding electronic dynamics on material surfaces is fundamentally important for applications including nanoelectronics, inhomogeneous catalysis, and photovoltaics. Practical approaches based on time-dependent density functional theory for open systems have been developed to characterize the dissipative dynamics of electrons in bulk materials. The accuracy and reliability of such approaches depend critically on how the electronic structure and memory effects of surrounding material environment are accounted for. In this work, we develop a novel squared-Lorentzian decomposition scheme, which preserves the positive semi-definiteness of the environment spectral matrix. The resulting electronic dynamics is guaranteed to be both accurate and convergent even in the long-time limit. The long-time stability of electronic dynamics simulation is thus greatly improved within the current decomposition scheme. The validity and usefulness of our new approach are exemplified via two prototypical model systems: quasi-one-dimensional atomic chains and two-dimensional bilayer graphene.
Correlation of Theory and Function in Well-Defined Bimetallic Electrocatalysts - Final Report
Crooks, Richard M.
2014-06-05
The objective of this research proposal was to correlate the structure of nanoparticles that are comprised of ~100-200 atoms to their electrocatalytic function. This objective was based on the growing body of evidence suggesting that catalytic properties can be tailored through controlled synthesis of nanoparticles. What has been missing from many of these studies, and what we are contributing, is a model catalyst that is sufficiently small, structurally well-defined, and well-characterized that its function can be directly predicted by theory. Specifically, our work seeks to develop a fundamental and detailed understanding of the relationship between the structure of nanoscopic oxygen-reduction catalysts and their function. We assembled a team with expertise in theory, synthesis, and advanced characterization methods to address the primary objective of this project. We anticipated the outcomes of the study to be: (1) a better theoretical understanding of how nanoparticle structure affects catalytic properties; (2) the development of advanced, in-situ and ex-situ, atomic-scale characterization methods that are appropriate for particles containing about 100 atoms; and (3) improved synthetic methods that produce unique nanoparticle structures that can be used to test theoretical predictions. During the project period, we have made excellent progress on all three fronts.
Davis, A. B.; Marshak, A.; Cahalan, R. F.
2001-01-01
We survey radiative Green function theory (1) in linear transport theory where numerical procedures are required to obtain specific results and (2) in the photon diffusion limit (large optical depths) where it is analytically tractable, at least for homogeneous plane-parallel media. We then describe two recent applications of Green function theory to passive cloud remote sensing in the presence of strong three-dimensional transport effects. Finally, we describe recent instrumental breakthroughs in 'off-beam' cloud lidar which is based on direct measurements of radiative Green functions with special attention to the data collected during the Shuttle-based Lidar In-space Technology Experiment (LITE) mission.
Wang, Jianwei; Zhang, Yong; Wang, Lin-Wang
2015-07-31
We propose a systematic approach that can empirically correct three major errors typically found in a density functional theory (DFT) calculation within the local density approximation (LDA) simultaneously for a set of common cation binary semiconductors, such as III-V compounds, (Ga or In)X with X = N,P,As,Sb, and II-VI compounds, (Zn or Cd)X, with X = O,S,Se,Te. By correcting (1) the binary band gaps at high-symmetry points , L, X, (2) the separation of p-and d-orbital-derived valence bands, and (3) conduction band effective masses to experimental values and doing so simultaneously for common cation binaries, the resulting DFT-LDA-based quasi-first-principles method can be used to predict the electronic structure of complex materials involving multiple binaries with comparable accuracy but much less computational cost than a GW level theory. This approach provides an efficient way to evaluate the electronic structures and other material properties of complex systems, much needed for material discovery and design.
Theory of light-harvesting in photosynthesis: from structure to function |
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
MIT-Harvard Center for Excitonics Theory of light-harvesting in photosynthesis: from structure to function May 17, 2011 at 3pm/36-428 Thomas Renger Johannes Kepler Universitat -Linz, Austria renger2 abstract In photosynthesis, light energy absorbed in light-harvesting pigment-protein complexes is transferred via an exciton mechanism to the reaction center where it is used to drive electron transfer reactions. The quantum efficiency of the transfer is close to 100 percent, that is, almost all
DFT investigation on the electronic structure of Faujasite
Popeneciu, Horea; Calborean, Adrian; Tudoran, Cristian; Buimaga-Iarinca, Luiza
2013-11-13
We report here first-principle pseudopotential DFT calculations to investigate relevant aspects of the electronic structure of zeolites based FAU. Fundamental molecular issues of the band-gap and electronic population analysis were reviewed under GGA/RPBE level of theory, corroborated with a DZP basis set and Troullier-Martins norm conserving pseudo-potentials. The atom-projected density of states and the analysis of HOMO-LUMO frontier orbitals at Gamma point were performed. Their electronic transfers are discussed through the alignment and relative positions of orbitals in order to determine the way that the molecule interacts with adsorbed molecules and other practical applications. Mulliken population analysis was employed for describing atomic charge distribution in the chosen systems.
Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Gunawardana, K. G.S.H.; Song, Xueyu
2014-12-22
Recently developed fundamental measure density functional theory (FMT) is used to study binary hard sphere (HS) complexes in crystalline phases. By comparing the excess free energy, pressure and phase diagram, we show that the fundamental measure functional yields good agreements to the available simulation results of AB, AB2 and AB13 crystals. Additionally, we use this functional to study the HS models of five binary crystals, Cu5Zr(C15b), Cu51Zr14(β), Cu10Zr7(φ), CuZr(B2) and CuZr2 (C11b), which are observed in the Cu-Zr system. The FMT functional gives well behaved minimum for most of the hard sphere crystal complexes in the two dimensional Gaussian space,more » namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu10Zr7(φ). We argue that the observed solid phases for the HS models of the Cu-Zr system are true thermodynamic stable phases and can be used as a reference system in perturbation calculations.« less
Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory
Gunawardana, K. G.S.H.; Song, Xueyu
2014-12-22
Recently developed fundamental measure density functional theory (FMT) is used to study binary hard sphere (HS) complexes in crystalline phases. By comparing the excess free energy, pressure and phase diagram, we show that the fundamental measure functional yields good agreements to the available simulation results of AB, AB_{2} and AB_{13} crystals. Additionally, we use this functional to study the HS models of five binary crystals, Cu_{5}Zr(C15_{b}), Cu_{51}Zr_{14}(?), Cu_{10}Zr_{7}(?), CuZr(B2) and CuZr_{2} (C11_{b}), which are observed in the Cu-Zr system. The FMT functional gives well behaved minimum for most of the hard sphere crystal complexes in the two dimensional Gaussian space, namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu_{10}Zr_{7}(?). We argue that the observed solid phases for the HS models of the Cu-Zr system are true thermodynamic stable phases and can be used as a reference system in perturbation calculations.
Quasi-particle energy spectra in local reduced density matrix functional theory
Lathiotakis, Nektarios N.; Helbig, Nicole; Rubio, Angel
2014-10-28
Recently, we introduced [N. N. Lathiotakis, N. Helbig, A. Rubio, and N. I. Gidopoulos, Phys. Rev. A 90, 032511 (2014)] local reduced density matrix functional theory (local RDMFT), a theoretical scheme capable of incorporating static correlation effects in Kohn-Sham equations. Here, we apply local RDMFT to molecular systems of relatively large size, as a demonstration of its computational efficiency and its accuracy in predicting single-electron properties from the eigenvalue spectrum of the single-particle Hamiltonian with a local effective potential. We present encouraging results on the photoelectron spectrum of molecular systems and the relative stability of C{sub 20} isotopes. In addition, we propose a modelling of the fractional occupancies as functions of the orbital energies that further improves the efficiency of the method useful in applications to large systems and solids.
Size-dependent error of the density functional theory ionization potential in vacuum and solution
Sosa Vazquez, Xochitl A.; Isborn, Christine M.
2015-12-22
Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potential for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. As a result, in vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.
Size-dependent error of the density functional theory ionization potential in vacuum and solution
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Sosa Vazquez, Xochitl A.; Isborn, Christine M.
2015-12-22
Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. As a result, in vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less
McDonnell, J. D.; Schunck, N.; Higdon, D.; Sarich, J.; Wild, S. M.; Nazarewicz, W.
2015-03-24
Statistical tools of uncertainty quantification can be used to assess the information content of measured observables with respect to present-day theoretical models, to estimate model errors and thereby improve predictive capability, to extrapolate beyond the regions reached by experiment, and to provide meaningful input to applications and planned measurements. To showcase new opportunities offered by such tools, we make a rigorous analysis of theoretical statistical uncertainties in nuclear density functional theory using Bayesian inference methods. By considering the recent mass measurements from the Canadian Penning Trap at Argonne National Laboratory, we demonstrate how the Bayesian analysis and a direct least-squares optimization, combined with high-performance computing, can be used to assess the information content of the new data with respect to a model based on the Skyrme energy density functional approach. Employing the posterior probability distribution computed with a Gaussian process emulator, we apply the Bayesian framework to propagate theoretical statistical uncertainties in predictions of nuclear masses, two-neutron dripline, and fission barriers. Overall, we find that the new mass measurements do not impose a constraint that is strong enough to lead to significant changes in the model parameters. In addition, the example discussed in this study sets the stage for quantifying and maximizing the impact of new measurements with respect to current modeling and guiding future experimental efforts, thus enhancing the experiment-theory cycle in the scientific method.
McDonnell, J. D.; Schunck, N.; Higdon, D.; Sarich, J.; Wild, S. M.; Nazarewicz, W.
2015-03-24
Statistical tools of uncertainty quantification can be used to assess the information content of measured observables with respect to present-day theoretical models, to estimate model errors and thereby improve predictive capability, to extrapolate beyond the regions reached by experiment, and to provide meaningful input to applications and planned measurements. To showcase new opportunities offered by such tools, we make a rigorous analysis of theoretical statistical uncertainties in nuclear density functional theory using Bayesian inference methods. By considering the recent mass measurements from the Canadian Penning Trap at Argonne National Laboratory, we demonstrate how the Bayesian analysis and a direct least-squares optimization, combined with high-performance computing, can be used to assess the information content of the new data with respect to a model based on the Skyrme energy density functional approach. Employing the posterior probability distribution computed with a Gaussian process emulator, we apply the Bayesian framework to propagate theoretical statistical uncertainties in predictions of nuclear masses, two-neutron dripline, and fission barriers. Overall, we find that the new mass measurements do not impose a constraint that is strong enough to lead to significant changes in the model parameters. As a result, the example discussed in this study sets the stage for quantifying and maximizing the impact of new measurements with respect to current modeling and guiding future experimental efforts, thus enhancing the experiment-theory cycle in the scientific method.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
McDonnell, J. D.; Schunck, N.; Higdon, D.; Sarich, J.; Wild, S. M.; Nazarewicz, W.
2015-03-24
Statistical tools of uncertainty quantification can be used to assess the information content of measured observables with respect to present-day theoretical models, to estimate model errors and thereby improve predictive capability, to extrapolate beyond the regions reached by experiment, and to provide meaningful input to applications and planned measurements. To showcase new opportunities offered by such tools, we make a rigorous analysis of theoretical statistical uncertainties in nuclear density functional theory using Bayesian inference methods. By considering the recent mass measurements from the Canadian Penning Trap at Argonne National Laboratory, we demonstrate how the Bayesian analysis and a direct least-squaresmore » optimization, combined with high-performance computing, can be used to assess the information content of the new data with respect to a model based on the Skyrme energy density functional approach. Employing the posterior probability distribution computed with a Gaussian process emulator, we apply the Bayesian framework to propagate theoretical statistical uncertainties in predictions of nuclear masses, two-neutron dripline, and fission barriers. Overall, we find that the new mass measurements do not impose a constraint that is strong enough to lead to significant changes in the model parameters. In addition, the example discussed in this study sets the stage for quantifying and maximizing the impact of new measurements with respect to current modeling and guiding future experimental efforts, thus enhancing the experiment-theory cycle in the scientific method.« less
Orbital-free density functional theory implementation with the projector augmented-wave method
Lehtomki, Jouko; Makkonen, Ilja; Harju, Ari; Lopez-Acevedo, Olga; Caro, Miguel A.
2014-12-21
We present a computational scheme for orbital-free density functional theory (OFDFT) that simultaneously provides access to all-electron values and preserves the OFDFT linear scaling as a function of the system size. Using the projector augmented-wave method (PAW) in combination with real-space methods, we overcome some obstacles faced by other available implementation schemes. Specifically, the advantages of using the PAW method are twofold. First, PAW reproduces all-electron values offering freedom in adjusting the convergence parameters and the atomic setups allow tuning the numerical accuracy per element. Second, PAW can provide a solution to some of the convergence problems exhibited in other OFDFT implementations based on Kohn-Sham (KS) codes. Using PAW and real-space methods, our orbital-free results agree with the reference all-electron values with a mean absolute error of 10 meV and the number of iterations required by the self-consistent cycle is comparable to the KS method. The comparison of all-electron and pseudopotential bulk modulus and lattice constant reveal an enormous difference, demonstrating that in order to assess the performance of OFDFT functionals it is necessary to use implementations that obtain all-electron values. The proposed combination of methods is the most promising route currently available. We finally show that a parametrized kinetic energy functional can give lattice constants and bulk moduli comparable in accuracy to those obtained by the KS PBE method, exemplified with the case of diamond.
Franke, J.-H.; Kosov, D. S.
2013-12-14
The adsorption of the chiral molecule lactate on the intrinsically chiral noble metal surfaces Pt(321), Au(321), and Ag(321) is studied by density functional theory calculations. We use the oPBE-vdW functional which includes van der Waals forces on an ab initio level. It is shown that the molecule binds via its carboxyl and the hydroxyl oxygen atoms to the surface. The binding energy is larger on Pt(321) and Ag(321) than on Au(321). An analysis of the contributions to the binding energy of the different molecular functional groups reveals that the deprotonated carboxyl group contributes most to the binding energy, with a much smaller contribution of the hydroxyl group. The Pt(321) surface shows considerable enantioselectivity of 0.06 eV. On Au(321) and Ag(321) it is much smaller if not vanishing. The chiral selectivity of the Pt(321) surface can be explained by two factors. First, it derives from the difference in van der Waals attraction of L- and D-lactate to the surface that we trace to differences in the binding energy of the methyl group. Second, the multi-point binding pattern for lactate on the Pt(321) surface is sterically more sensitive to surface chirality and also leads to large binding energy contributions of the hydroxyl group. We also calculate the charge transfer to the molecule and the work function to gauge changes in electronic structure of the adsorbed molecule. The work function is lowered by 0.8 eV on Pt(321) with much smaller changes on Au(321) and Ag(321)
Solving the Self-Interaction Problem in Kohn-Sham Density Functional Theory. Application to Atoms
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Daene, M.; Gonis, A.; Nicholson, D. M.; Stocks, G. M.
2014-10-14
Previously, we proposed a computational methodology that addresses the elimination of the self-interaction error from the Kohn–Sham formulation of the density functional theory. We demonstrated how the exchange potential can be obtained, and presented results of calculations for atomic systems up to Kr carried out within a Cartesian coordinate system. In our paper, we provide complete details of this self-interaction free method formulated in spherical coordinates based on the explicit equidensity basis ansatz. We also prove analytically that derivatives obtained using this method satisfy the Virial theorem for spherical orbitals, where the problem can be reduced to one dimension. Wemore » present the results of calculations of ground-state energies of atomic systems throughout the periodic table carried out within the exchange-only mode.« less
Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory
Zhang, DaDi; Zheng, Xiao; Li, Chen; Yang, Weitao
2015-04-21
We explore effects of orbital relaxation on Kohn–Sham frontier orbital energies in density functional theory by using a nonempirical scaling correction approach developed in Zheng et al. [J. Chem. Phys. 138, 174105 (2013)]. Relaxation of Kohn–Sham orbitals upon addition/removal of a fractional number of electrons to/from a finite system is determined by a systematic perturbative treatment. The information of orbital relaxation is then used to improve the accuracy of predicted Kohn–Sham frontier orbital energies by Hartree–Fock, local density approximation, and generalized gradient approximation methods. The results clearly highlight the significance of capturing the orbital relaxation effects. Moreover, the proposed scaling correction approach provides a useful way of computing derivative gaps and Fukui quantities of N-electron finite systems (N is an integer), without the need to perform self-consistent-field calculations for (N ± 1)-electron systems.
Fattebert, J; Law, R J; Bennion, B; Lau, E Y; Schwegler, E; Lightstone, F C
2009-04-24
We evaluate the accuracy of density functional theory quantum calculations of biomolecular subsystems using a simple electrostatic embedding scheme. Our scheme is based on dividing the system of interest into a primary and secondary subsystem. A finite difference discretization of the Kohn-Sham equations is used for the primary subsystem, while its electrostatic environment is modeled with a simple one-electron potential. Force-field atomic partial charges are used to generate smeared Gaussian charge densities and to model the secondary subsystem. We illustrate the utility of this approach with calculations of truncated dipeptide chains. We analyze quantitatively the accuracy of this approach by calculating atomic forces and comparing results with fullQMcalculations. The impact of the choice made in terminating dangling bonds at the frontier of the QM region is also investigated.
Density functional theory calculations of magnetocrystalline anisotropy energies for (Fe1-xCox)2B
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Daene, Markus; Kim, Soo Kyung; Surh, Michael P.; Aberg, Daniel; Benedict, Lorin X.
2015-06-15
We present and discuss density functional theory calculations of magnetic properties of the family of ferromagnetic compounds, (Fe1-xCox)2B, focusing specifically on the magnetocrystalline anisotropy energy (MAE). Using periodic supercells of various sizes (up to 96 atoms), it is shown that the general qualitative features of the composition dependence of the MAE is in agreement with experimental findings, while our predicted magnitudes are larger than those of experiment. We find that the use of small supercells (6 and 12-atom) favors larger MAE values relative to a statistical sample of configurations constructed with 96-atom supercells. As a result, the effect of latticemore » relaxations is shown to be small. Calculations of the Curie temperature for this alloy are also presented.« less
DFT Investigation of the Catalytic Hydromethylation ofalpha-Olefins bvy
Office of Scientific and Technical Information (OSTI)
Metallocenes. 1. Difference betrween Scandium andLutetium in Propene Hydromethylation (Journal Article) | SciTech Connect DFT Investigation of the Catalytic Hydromethylation ofalpha-Olefins bvy Metallocenes. 1. Difference betrween Scandium andLutetium in Propene Hydromethylation Citation Details In-Document Search Title: DFT Investigation of the Catalytic Hydromethylation ofalpha-Olefins bvy Metallocenes. 1. Difference betrween Scandium andLutetium in Propene Hydromethylation A DFT study of
Current density partitioning in time-dependent current density functional theory
Mosquera, Martín A.; Wasserman, Adam; Department of Physics, Purdue University, West Lafayette, Indiana 47907
2014-05-14
We adapt time-dependent current density functional theory to allow for a fragment-based solution of the many-electron problem of molecules in the presence of time-dependent electric and magnetic fields. Regarding a molecule as a set of non-interacting subsystems that individually evolve under the influence of an auxiliary external electromagnetic vector-scalar potential pair, the partition 4-potential, we show that there are one-to-one mappings between this auxiliary potential, a sharply-defined set of fragment current densities, and the total current density of the system. The partition electromagnetic (EM) 4-potential is expressed in terms of the real EM 4-potential of the system and a gluing EM 4-potential that accounts for exchange-correlation effects and mutual interaction forces between fragments that are required to yield the correct electron dynamics. We prove the zero-force theorem for the fragmented system, establish a variational formulation in terms of action functionals, and provide a simple illustration for a charged particle in a ring.
Filatov, Michael; Huix-Rotllant, Miquel; Burghardt, Irene
2015-05-14
State-averaged (SA) variants of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, SA-REKS and state-interaction (SI)-SA-REKS, implement ensemble density functional theory for variationally obtaining excitation energies of molecular systems. In this work, the currently existing version of the SA-REKS method, which included only one excited state into the ensemble averaging, is extended by adding more excited states to the averaged energy functional. A general strategy for extension of the REKS-type methods to larger ensembles of ground and excited states is outlined and implemented in extended versions of the SA-REKS and SI-SA-REKS methods. The newly developed methods are tested in the calculation of several excited states of ground-state multi-reference systems, such as dissociating hydrogen molecule, and excited states of donor–acceptor molecular systems. For hydrogen molecule, the new method correctly reproduces the distance dependence of the lowest excited state energies and describes an avoided crossing between the doubly excited and singly excited states. For bithiophene–perylenediimide stacked complex, the SI-SA-REKS method correctly describes crossing between the locally excited state and the charge transfer excited state and yields vertical excitation energies in good agreement with the ab initio wavefunction methods.
Session #1: Cutting Edge Methodologies--Beyond Current DFT
Broader source: Energy.gov [DOE]
Benchmarking state-of-the-art approaches, accurate energy landscape. Identify problems with the current DFT-LDA and GGA approaches and possible pathways to overcome these problems.
DFT Investigation of the Catalytic Hydromethylation ofalpha-Olefins...
Office of Scientific and Technical Information (OSTI)
DFT Investigation of the Catalytic Hydromethylation ofalpha-Olefins bvy Metallocenes. 1. Difference betrween Scandium andLutetium in Propene Hydromethylation Citation Details ...
cDF Theory Software for mesoscopic modeling of equilibrium and transport phenomena
Energy Science and Technology Software Center (OSTI)
2015-12-01
The approach is based on classical Density Functional Theory ((cDFT) coupled with the Poisson-Nernst-Planck (PNP) transport kinetics model and quantum mechanical description of short-range interaction and elementary transport processes. The model we proposed and implemented is fully atomistic, taking into account pairwise short-range and manybody long-range interactions. But in contrast to standard molecular dynamics (MD) simulations, where long-range manybody interactions are evaluated as a sum of pair-wise atom-atom contributions, we include them analytically based onmore » wellestablished theories of electrostatic and excluded volume interactions in multicomponent systems. This feature of the PNP/cDFT approach allows us to reach well beyond the length-scales accessible to MD simulations, while retaining the essential physics of interatomic interactions from first principles and in a parameter-free fashion.« less
Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Berardo, Enrico; Hu, Han -Shi; van Dam, Hubertus J. J.; Shevlin, Stephen A.; Woodley, Scott M.; Kowalski, Karol; Zwijnenburg, Martijn A.
2014-02-26
We have investigated the description of excited state relaxation in naked and hydrated TiO2 nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be themore » inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO2 nanoparticles is predicted to be associated with a large Stokes’ shift.« less
Representing the thermal state in time-dependent density functional theory
Modine, N. A.; Hatcher, R. M.
2015-05-28
Classical molecular dynamics (MD) provides a powerful and widely used approach to determining thermodynamic properties by integrating the classical equations of motion of a system of atoms. Time-Dependent Density Functional Theory (TDDFT) provides a powerful and increasingly useful approach to integrating the quantum equations of motion for a system of electrons. TDDFT efficiently captures the unitary evolution of a many-electron state by mapping the system into a fictitious non-interacting system. In analogy to MD, one could imagine obtaining the thermodynamic properties of an electronic system from a TDDFT simulation in which the electrons are excited from their ground state by a time-dependent potential and then allowed to evolve freely in time while statistical data are captured from periodic snapshots of the system. For a variety of systems (e.g., many metals), the electrons reach an effective state of internal equilibrium due to electron-electron interactions on a time scale that is short compared to electron-phonon equilibration. During the initial time-evolution of such systems following electronic excitation, electron-phonon interactions should be negligible, and therefore, TDDFT should successfully capture the internal thermalization of the electrons. However, it is unclear how TDDFT represents the resulting thermal state. In particular, the thermal state is usually represented in quantum statistical mechanics as a mixed state, while the occupations of the TDDFT wave functions are fixed by the initial state in TDDFT. Two key questions involve (1) reformulating quantum statistical mechanics so that thermodynamic expectations can be obtained as an unweighted average over a set of many-body pure states and (2) constructing a family of non-interacting (single determinant) TDDFT states that approximate the required many-body states for the canonical ensemble. In Section II, we will address these questions by first demonstrating that thermodynamic expectations can be evaluated by averaging over certain many-body pure states, which we will call thermal states, and then constructing TDDFT states that approximate these thermal states. In Section III, we will present some numerical tests of the resulting theory, and in Section IV, we will summarize our main results and discuss some possible future directions for this work.
Representing the thermal state in time-dependent density functional theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Modine, N. A.; Hatcher, R. M.
2015-05-28
Classical molecular dynamics (MD) provides a powerful and widely used approach to determining thermodynamic properties by integrating the classical equations of motion of a system of atoms. Time-Dependent Density Functional Theory (TDDFT) provides a powerful and increasingly useful approach to integrating the quantum equations of motion for a system of electrons. TDDFT efficiently captures the unitary evolution of a many-electron state by mapping the system into a fictitious non-interacting system. In analogy to MD, one could imagine obtaining the thermodynamic properties of an electronic system from a TDDFT simulation in which the electrons are excited from their ground state bymore » a time-dependent potential and then allowed to evolve freely in time while statistical data are captured from periodic snapshots of the system. For a variety of systems (e.g., many metals), the electrons reach an effective state of internal equilibrium due to electron-electron interactions on a time scale that is short compared to electron-phonon equilibration. During the initial time-evolution of such systems following electronic excitation, electron-phonon interactions should be negligible, and therefore, TDDFT should successfully capture the internal thermalization of the electrons. However, it is unclear how TDDFT represents the resulting thermal state. In particular, the thermal state is usually represented in quantum statistical mechanics as a mixed state, while the occupations of the TDDFT wave functions are fixed by the initial state in TDDFT. Two key questions involve (1) reformulating quantum statistical mechanics so that thermodynamic expectations can be obtained as an unweighted average over a set of many-body pure states and (2) constructing a family of non-interacting (single determinant) TDDFT states that approximate the required many-body states for the canonical ensemble. In Section II, we will address these questions by first demonstrating that thermodynamic expectations can be evaluated by averaging over certain many-body pure states, which we will call thermal states, and then constructing TDDFT states that approximate these thermal states. In Section III, we will present some numerical tests of the resulting theory, and in Section IV, we will summarize our main results and discuss some possible future directions for this work.« less
Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter A.; Li, Sha; Mavrikakis, Manos
2014-12-05
We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.
Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study
Sangha, A. K.; Parks, J. M.; Standaert, R. F.; Ziebell, A.; Davis, M.; Smith, J. C.
2012-04-26
Lignin is a complex, heterogeneous polymer in plant cell walls that provides mechanical strength to the plant stem and confers resistance to degrading microbes, enzymes, and chemicals. Lignin synthesis initiates through oxidative radical-radical coupling of monolignols, the most common of which are p-coumaryl, coniferyl, and sinapyl alcohols. Here, we use density functional theory to characterize radical-radical coupling reactions involved in monolignol dimerization. We compute reaction enthalpies for the initial self- and cross-coupling reactions of these monolignol radicals to form dimeric intermediates via six major linkages observed in natural lignin. The 8-O-4, 8-8, and 8-5 coupling are computed to be the most favorable, whereas the 5-O-4, 5-5, and 8-1 linkages are less favorable. Overall, p-coumaryl self- and cross-coupling reactions are calculated to be the most favorable. For cross-coupling reactions, in which each radical can couple via either of the two sites involved in dimer formation, the more reactive of the two radicals is found to undergo coupling at its site with the highest spin density.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Ganesh, Panchapakesan; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A; Kent, Paul R
2014-01-01
Highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges suchmore » as DFT-D are inaccurate unless the local charge transfer is assessed. The results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.« less
Gautam, P.; Gautam, D.; Chaudhary, R. P.
2013-12-15
The title compound N-(4-acetyl-5,5-dimethyl-4,5-dihydro-1,3,4-thiadiazol-2-yl)acetamide (III) was obtained from the reaction of 2-(propan-2-ylidene)hydrazinecarbothioamide (II) with acetic anhydride instead of formation of the desired thiosemcarbazide derivative of Meldrum acid. The structures of II and III were established by elemental analysis, IR, NMR, Mass and X-ray crystallographic studies. II crystallizes in triclinic system, sp. gr. P-bar1 Z = 2; III crystallizes in the monoclinic system, sp. gr. P2{sub 1}/c, Z = 8. Density functional theory (DFT) calculations have been carried out for III. {sup 1}H and {sup 13}C NMR of III has been calculated and correlated with experimental results.
Microsoft PowerPoint - DFT Syngas Cleanup_3
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
Density Functional Theory Study of Syngas Cleanup with Ceria-Based Rare Earth Oxides Matthew D. Krcha 1 , Adam D. Mayernick 1 , Michael J. Janik 1 , Kerry M. Dooley 2 1 Department...
Magnetism in undoped ZnS studied from density functional theory
Xiao, Wen-Zhi E-mail: llwang@hun.edu.cn; Rong, Qing-Yan; Xiao, Gang; Wang, Ling-ling E-mail: llwang@hun.edu.cn; Meng, Bo
2014-06-07
The magnetic property induced by the native defects in ZnS bulk, thin film, and quantum dots are investigated comprehensively based on density functional theory within the generalized gradient approximation + Hubbard U (GGA?+?U) approach. We find the origin of magnetism is closely related to the introduction of hole into ZnS systems. The relative localization of S-3p orbitals is another key to resulting in unpaired p-electron, due to Hund's rule. For almost all the ZnS systems under study, the magnetic moment arises from the S-dangling bonds generated by Zn vacancies. The charge-neutral Zn vacancy, Zn vacancy in 1? charge sate, and S vacancy in the 1+ charge sate produce a local magnetic moment of 2.0, 1.0, and 1.0??{sub B}, respectively. The Zn vacancy in the neutral and 1? charge sates are the important cause for the ferromagnetism in ZnS bulk, with a Curie temperature (T{sub C}) above room temperature. For ZnS thin film with clean (111) surfaces, the spins on each surface are ferromagnetically coupled but antiferromagnetically coupled between two surfaces, which is attributable to the internal electric field between the two polar (111) surfaces of the thin film. Only surface Zn vacancies can yield local magnetic moment for ZnS thin film and quantum dot, which is ascribed to the surface effect. Interactions between magnetic moments on S-3p states induced by hole-doping are responsible for the ferromagnetism observed experimentally in various ZnS samples.
Representing the thermal state in time-dependent density functional theory
Modine, N. A.; Hatcher, R. M.
2015-05-28
Classical molecular dynamics (MD) provides a powerful and widely used approach to determining thermodynamic properties by integrating the classical equations of motion of a system of atoms. Time-Dependent Density Functional Theory (TDDFT) provides a powerful and increasingly useful approach to integrating the quantum equations of motion for a system of electrons. TDDFT efficiently captures the unitary evolution of a many-electron state by mapping the system into a fictitious non-interacting system. In analogy to MD, one could imagine obtaining the thermodynamic properties of an electronic system from a TDDFT simulation in which the electrons are excited from their ground state by a time-dependent potential and then allowed to evolve freely in time while statistical data are captured from periodic snapshots of the system. For a variety of systems (e.g., many metals), the electrons reach an effective state of internal equilibrium due to electron-electron interactions on a time scale that is short compared to electron-phonon equilibration. During the initial time-evolution of such systems following electronic excitation, electron-phonon interactions should be negligible, and therefore, TDDFT should successfully capture the internal thermalization of the electrons. However, it is unclear how TDDFT represents the resulting thermal state. In particular, the thermal state is usually represented in quantum statistical mechanics as a mixed state, while the occupations of the TDDFT wavefunctions are fixed by the initial state in TDDFT. We work to address this puzzle by (A) reformulating quantum statistical mechanics so that thermodynamic expectations can be obtained as an unweighted average over a set of many-body pure states and (B) constructing a family of non-interacting (single determinant) TDDFT states that approximate the required many-body states for the canonical ensemble.
The magnetic and electronic structure of vanadyl pyrophosphate from density functional theory
Cheng, Mu-Jeng; Nielsen, Robert J.; Tahir-Kheli, Jamil; Goddard III, William A.
2011-01-01
We have studied the magnetic structure of the high symmetry vanadyl pyrophosphate ((VO)?P?O?, VOPO), focusing on the spin exchange couplings, using density functional theory (B3LYP) with the full three-dimensional periodicity. VOPO involves four distinct spin couplings: two larger couplings exist along the chain direction (a-axis), which we predict to be antiferromagnetic, J_{OPO} = ?156.8 K and J_{O} = ?68.6 K, and two weaker couplings appear along the c (between two layers) and b directions (between two chains in the same layer), which we calculate to be ferromagnetic, J_{layer} = 19.2 K and J_{chain} = 2.8 K. Based on the local density of states and the response of spin couplings to varying the cell parameter a, we found that J_{OPO} originates from a super-exchange interaction through the bridging OPO unit. In contrast, J_{O} results from a direct overlap of 3d_{x?y } orbitals on two vanadium atoms in the same V_{2}O_{8} motif, making it very sensitive to structural fluctuations. Based on the variations in VO bond length as a function of strain along a, we found that the VO bonds of V(OPO)_{2}V are covalent and rigid, whereas the bonds of V(O)_{2}V are fragile and dative. These distinctions suggest that compression along the a-axis would have a dramatic impact on J_{O}, changing the magnetic structure and spin gap of VOPO. This result also suggests that assuming J_{O} to be a constant over the range of 2300 K whilst fitting couplings to the experimental magnetic susceptibility is an invalid method. Regarding its role as a catalyst, the bonding pattern suggests that O_{2} can penetrate beyond the top layers of the VOPO surface, converting multiple V atoms from the +4 to +5 oxidation state, which seems crucial to explain the deep oxidation of n-butane to maleic anhydride.
Staszczak, A,
2013-01-01
Background: The reactions with the neutron-rich 48Ca beam and actinide targets resulted in the detection of new superheavy (SH) nuclides with Z=104 118. The unambiguous identification of the new isotopes, however, still poses a problem because their -decay chains terminate by spontaneous fission (SF) before reaching the known region of the nuclear chart. The understanding of the competition between -decay and SF channels in SH nuclei is, therefore, of crucial importance for our ability to map the SH region and to assess its extent.
Purpose: We perform self-consistent calculations of the competing decay modes of even-even SH isotopes with 108 Z 126 and 148 N 188.
Methods: We use the state-of-the-art computational framework based on self-consistent symmetry-unrestricted nuclear density functional theory capable of describing the competition between nuclear attraction and electrostatic repulsion. We apply the SkM* Skyrme energy density functional. The collective mass tensor of the fissioning superfluid nucleus is computed by means of the cranking approximation to the adiabatic time-dependent Hartree-Fock-Bogoliubov (HFB) approach. This paper constitutes a systematic self-consistent study of spontaneous fission in the SH region, carried out at a full HFB level, that simultaneously takes into account both triaxiality and reflection asymmetry.
Results: Breaking axial symmetry and parity turns out to be crucial for a realistic estimate of collective action; it results in lowering SF lifetimes by more than 7 orders of magnitude in some cases. We predict two competing SF modes: reflection symmetric modes and reflection asymmetric modes.
Conclusions: The shortest-lived SH isotopes decay by SF; they are expected to lie in a narrow corridor formed by 280Hs, 284Fl, and 118284Uuo that separates the regions of SH nuclei synthesized in cold-fusion and hot-fusion reactions. The region of long-lived SH nuclei is expected to be centered on 294Ds with a total half-life of 1.5 days. Our survey provides a solid benchmark for the future improvements of self-consistent SF calculations in the region of SH nuclei.
Degenerate ground states and nonunique potentials: Breakdown and restoration of density functionals
Capelle, K.; Ullrich, C. A.; Vignale, G.
2007-07-15
The Hohenberg-Kohn (HK) theorem is one of the most fundamental theorems of quantum mechanics, and constitutes the basis for the very successful density-functional approach to inhomogeneous interacting many-particle systems. Here we show that in formulations of density-functional theory (DFT) that employ more than one density variable, applied to systems with a degenerate ground state, there is a subtle loophole in the HK theorem, as all mappings between densities, wave functions, and potentials can break down. Two weaker theorems which we prove here, the joint-degeneracy theorem and the internal-energy theorem, restore the internal, total, and exchange-correlation energy functionals to the extent needed in applications of DFT to atoms, molecules, and solids. The joint-degeneracy theorem constrains the nature of possible degeneracies in general many-body systems.
Maranzana, Andrea E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it Giordana, Anna E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it Indarto, Antonius Tonachini, Glauco; Barone, Vincenzo E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it; Causà, Mauro E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it; Pavone, Michele E-mail: anna.giordana@hotmail.com E-mail: mauro.causa@unina.it
2013-12-28
Our purpose is to identify a computational level sufficiently dependable and affordable to assess trends in the interaction of a variety of radical or closed shell unsaturated hydro-carbons A adsorbed on soot platelet models B. These systems, of environmental interest, would unavoidably have rather large sizes, thus prompting to explore in this paper the performances of relatively low-level computational methods and compare them with higher-level reference results. To this end, the interaction of three complexes between non-polar species, vinyl radical, ethyne, or ethene (A) with benzene (B) is studied, since these species, involved themselves in growth processes of polycyclic aromatic hydrocarbons (PAHs) and soot particles, are small enough to allow high-level reference calculations of the interaction energy ΔE{sub AB}. Counterpoise-corrected interaction energies ΔE{sub AB} are used at all stages. (1) Density Functional Theory (DFT) unconstrained optimizations of the A−B complexes are carried out, using the B3LYP-D, ωB97X-D, and M06-2X functionals, with six basis sets: 6-31G(d), 6-311 (2d,p), and 6-311++G(3df,3pd); aug-cc-pVDZ and aug-cc-pVTZ; N07T. (2) Then, unconstrained optimizations by Møller-Plesset second order Perturbation Theory (MP2), with each basis set, allow subsequent single point Coupled Cluster Singles Doubles and perturbative estimate of the Triples energy computations with the same basis sets [CCSD(T)//MP2]. (3) Based on an additivity assumption of (i) the estimated MP2 energy at the complete basis set limit [E{sub MP2/CBS}] and (ii) the higher-order correlation energy effects in passing from MP2 to CCSD(T) at the aug-cc-pVTZ basis set, ΔE{sub CC-MP}, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ΔE{sub AB} with basis set are not large for the title molecules, and the three functionals perform rather satisfactorily even with rather small basis sets [6-31G(d) and N07T], exhibiting deviation from the computational reference of less than 1 kcal mol{sup −1}. The zero-point vibrational energy corrected estimates Δ(E{sub AB}+ZPE), obtained with the three functionals and the 6-31G(d) and N07T basis sets, are compared with experimental D{sub 0} measures, when available. In particular, this comparison is finally extended to the naphthalene and coronene dimers and to three π−π associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms)
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Gonis, A.; Zhang, X. G.; Stocks, G. M.; Nicholson, D. M.
2015-10-23
Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide a complete solution of the v-representability problem by establishing a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of themore » density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism.« less
Gonis, A.; Zhang, X. G.; Stocks, G. M.; Nicholson, D. M.
2015-10-23
Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide a complete solution of the v-representability problem by establishing a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of the density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism.
Yamaoka, Hitoshi; Schwier, Eike F.; Arita, Masashi; Shimada, Kenya; Tsujii, Naohito; Jarrige, Ignace; Jiang, Jian; Hayashi, Hirokazu; Iwasawa, Hideaki; Namatame, Hirofumi; Taniguchi, Masaki; Kitazawa, Hideaki
2015-03-30
The electronic structure of Ce₃Pd₂₀X₆ (X = Si, Ge) has been studied using detailed density functional theory (DFT) calculations and high-resolution photoelectron spectroscopy (PES) measurements. The orbital decomposition of the electronic structure by DFT calculations indicates that Ce atoms at the (8c) site surrounded by 16 Pd atoms have a more localized nature and a tendency to be magnetic. Ce atoms in the (4a) site surrounded by 12 Pd and 6 X atoms, on the other, show only a negligible magnetic moment. In the photoemission valence-band spectra we observe a strong f⁰ (Ce⁴⁺) component with a small fraction of f¹ (Ce³⁺) component. The spectral weight of f¹ component near the Fermi level Ce₃Pd₂₀Si₆ is stronger than that for Ce₃Pd₂₀Ge₆ at the 4d-4f resonance, suggesting stronger c-f hybridization in the former. This may hint to the origin of the large electronic specific coefficient of Ce₃Pd₂₀Si₆ compared to Ce₃Pd₂₀Ge₆.
Zhang, Fan; Nemeth, Karoly; Bareño, Javier; Dogan, Fulya; Bloom, Ira D.; Shaw, Leon L.
2016-01-01
The feasibility of synthesizing functionalized h-BN (FBN) via the reaction between molten LiOH and solid h-BN is studied for the first time and its first ever application as an electrode material in Li-ion batteries is evaluated. Density functional theory (DFT) calculations are performed to provide mechanistic understanding of the possible electrochemical reactions derived from the FBN. Various materials characterizations reveal that the melt-solid reaction can lead to exfoliation and functionalization of h-BN simultaneously, while electrochemical analysis proves that the FBN can reversibly store charges through surface redox reactions with good cycle stability and coulombic efficiency. DFT calculations have provided physical insights into the observed electrochemical properties derived from the FBN.
Building A Universal Nuclear Energy Density Functional (UNEDF)
Carlson, Joe, Los Alamos National Laboratory, Los Alamos, NM; Furnstahl, Dick, Ohio State University, Columbus, OH; Horoi, Mihai, Central Michigan University, Mount Pleasant, MI; Lusk, Rusty, Argonne National Laboratory, Argonne, IL; Nazarewicz, Witek, University of Tennessee, Knoxville, TN; Ng, Esmond, Berkeley National Laboratory, Berkeley, CA; Thompson, Ian, Lawrence Livermore National Laboratory, Livermore, CA; Vary, James, Iowa State University, Ames, Iowa
2012-09-30
During the period of Dec. 1 2006 â Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: first, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory. The main physics areas of UNEDF, defined at the beginning of the project, were: ab initio structure; ab initio functionals; DFT applications; DFT extensions; reactions.
Borges, P. D. E-mail: lscolfaro@txstate.edu; Scolfaro, L. E-mail: lscolfaro@txstate.edu
2014-12-14
The thermoelectric properties of indium nitride in the most stable wurtzite phase (w-InN) as a function of electron and hole concentrations and temperature were studied by solving the semiclassical Boltzmann transport equations in conjunction with ab initio electronic structure calculations, within Density Functional Theory. Based on maximally localized Wannier function basis set and the ab initio band energies, results for the Seebeck coefficient are presented and compared with available experimental data for n-type as well as p-type systems. Also, theoretical results for electric conductivity and power factor are presented. Most cases showed good agreement between the calculated properties and experimental data for w-InN unintentionally and p-type doped with magnesium. Our predictions for temperature and concentration dependences of electrical conductivity and power factor revealed a promising use of InN for intermediate and high temperature thermoelectric applications. The rigid band approach and constant scattering time approximation were utilized in the calculations.
Matanovic, Ivana; Atanassov, Plamen; Kiefer, Boris; Garzon, Fernando; Henson, Neil J.
2014-10-05
The structural equilibrium parameters, the adsorption energies, and the vibrational frequencies of the nitrogen molecule and the hydrogen atom adsorbed on the (111) surface of rhodium have been investigated using different generalized-gradient approximation (GGA), nonlocal correlation, meta-GGA, and hybrid functionals, namely, Perdew, Burke, and Ernzerhof (PBE), Revised-RPBE, vdW-DF, Tao, Perdew, Staroverov, and Scuseria functional (TPSS), and Heyd, Scuseria, and Ernzerhof (HSE06) functional in the plane wave formalism. Among the five tested functionals, nonlocal vdW-DF and meta-GGA TPSS functionals are most successful in describing energetics of dinitrogen physisorption to the Rh(111) surface, while the PBE functional provides the correct chemisorption energy for the hydrogen atom. It was also found that TPSS functional produces the best vibrational spectra of the nitrogen molecule and the hydrogen atom on rhodium within the harmonic formalism with the error of 22.62 and 21.1% for the NAN stretching and RhAH stretching frequency. Thus, TPSS functional was proposed as a method of choice for obtaining vibrational spectra of low weight adsorbates on metallic surfaces within the harmonic approximation. At the anharmonic level, by decoupling the RhAH and NAN stretching modes from the bulk phonons and by solving one- and two-dimensional Schrodinger equation associated with the RhAH, RhAN, and NAN potential energy we calculated the anharmonic correction for NAN and RhAH stretching modes as 231 cm21 and 277 cm21 at PBE level. Anharmonic vibrational frequencies calculated with the use of the hybrid HSE06 function are in best agreement with available experiments.
Quantum field theory in the presence of a medium: Green's function expansions
Kheirandish, Fardin; Salimi, Shahriar
2011-12-15
Starting from a Lagrangian and using functional-integration techniques, series expansions of Green's function of a real scalar field and electromagnetic field, in the presence of a medium, are obtained. The parameter of expansion in these series is the susceptibility function of the medium. Relativistic and nonrelativistic Langevin-type equations are derived. Series expansions for Lifshitz energy in finite temperature and for an arbitrary matter distribution are derived. Covariant formulations for both scalar and electromagnetic fields are introduced. Two illustrative examples are given.
Zhang, Yu; Biggs, Jason D.; Healion, Daniel; Govind, Niranjan; Mukamel, Shaul
2012-11-21
We report simulations of X-ray absorption near edge structure (XANES), resonant inelastic X-ray scattering (RIXS) and 1D stimulated X-ray Raman spectroscopy (SXRS) signals of cysteine at the oxygen, nitrogen and sulfur K and L2,3 edges. The simulated XANES signals from the restricted window time-dependent density functional theory (REW-TDDFT) and the static exchange (STEX) method are compared with experiments, showing that REW-TDDFT is more accurate and computationally less expensive than STEX. Simulated RIXS and 1D SXRS signals from REW-TDDFT give some insights on the correlation of different excitations in the molecule.
Kikkinides, E. S.; Monson, P. A.
2015-03-07
Building on recent developments in dynamic density functional theory, we have developed a version of the theory that includes hydrodynamic interactions. This is achieved by combining the continuity and momentum equations eliminating velocity fields, so the resulting model equation contains only terms related to the fluid density and its time and spatial derivatives. The new model satisfies simultaneously continuity and momentum equations under the assumptions of constant dynamic or kinematic viscosity and small velocities and/or density gradients. We present applications of the theory to spinodal decomposition of subcritical temperatures for one-dimensional and three-dimensional density perturbations for both a van der Waals fluid and for a lattice gas model in mean field theory. In the latter case, the theory provides a hydrodynamic extension to the recently studied dynamic mean field theory. We find that the theory correctly describes the transition from diffusive phase separation at short times to hydrodynamic behaviour at long times.
Communication: Self-interaction correction with unitary invariance in density functional theory
Pederson, Mark R.; Ruzsinszky, Adrienn; Perdew, John P.; Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122
2014-03-28
Standard spin-density functionals for the exchange-correlation energy of a many-electron ground state make serious self-interaction errors which can be corrected by the Perdew-Zunger self-interaction correction (SIC). We propose a size-extensive construction of SIC orbitals which, unlike earlier constructions, makes SIC computationally efficient, and a true spin-density functional. The SIC orbitals are constructed from a unitary transformation that is explicitly dependent on the non-interacting one-particle density matrix. When this SIC is applied to the local spin-density approximation, improvements are found for the atomization energies of molecules.
Describing excited state relaxation and localization in TiO_{2} nanoparticles using TD-DFT
Berardo, Enrico; Hu, Han -Shi; van Dam, Hubertus J. J.; Shevlin, Stephen A.; Woodley, Scott M.; Kowalski, Karol; Zwijnenburg, Martijn A.
2014-02-26
We have investigated the description of excited state relaxation in naked and hydrated TiO_{2} nanoparticles using Time-Dependent Density Functional Theory (TD-DFT) with three common hybrid exchange-correlation (XC) potentials; B3LYP, CAM-B3LYP and BHLYP. Use of TD-CAM-B3LYP and TD-BHLYP yields qualitatively similar results for all structures, which are also consistent with predictions of coupled cluster theory for small particles. TD-B3LYP, in contrast, is found to make rather different predictions; including apparent conical intersections for certain particles that are not observed with TD-CAM-B3LYP nor with TD-BHLYP. In line with our previous observations for vertical excitations, the issue with TD-B3LYP appears to be the inherent tendency of TD-B3LYP, and other XC potentials with no or a low percentage of Hartree-Fock Like Exchange, to spuriously stabilize the energy of charge-transfer (CT) states. Even in the case of hydrated particles, for which vertical excitations are generally well described with all XC potentials, the use of TD-B3LYP appears to result in CT-problems for certain particles. We hypothesize that the spurious stabilization of CT-states by TD-B3LYP even may drive the excited state optimizations to different excited state geometries than those obtained using TD-CAM-B3LYP or TD-BHLYP. In conclusion, focusing on the TD-CAM-B3LYP and TD-BHLYP results, excited state relaxation in naked and hydrated TiO_{2} nanoparticles is predicted to be associated with a large Stokes shift.
Banai, R. E.; Brownson, J. R. S.; Burton, L. A.; Walsh, A.; Choi, S. G. To, B.; Hofherr, F.; Sorgenfrei, T.; Crll, A.
2014-07-07
We report on the anisotropic optical properties of single-crystal tin monosulfide (SnS). The components ?{sub a}, ?{sub b}, and ?{sub c} of the pseudodielectric-function tensor (?)=(??)+i(??) spectra are taken from 0.73 to 6.45 eV by spectroscopic ellipsometry. The measured (?) spectra are in a good agreement with the results of the calculated dielectric response from hybrid density functional theory. The (?) spectra show the direct band-gap onset and a total of eight above-band-gap optical structures that are associated with the interband-transition critical points (CPs). We obtain accurate CP energies by fitting analytic CP expressions to second-energy-derivatives of the (?) data. Their probable electronic origins and implications for photovoltaic applications are discussed.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Gordon, Elijah E.; Xiang, Hongjun; Koehler, Jurgen; Whangbo, Myung -Hwan
2016-03-01
The spins of the low-spin Ir4+ (S = 1/2, d5) ions at the octahedral sites of the oxides Sr3NiIrO6, Sr2IrO4 and Na2IrO3 exhibit preferred orientations with respect to their IrO6 octahedra. We evaluated the magnetic anisotropies of these S = 1/2 ions on the basis of DFT calculations including spin-orbit coupling (SOC), and probed their origin by performing perturbation theory analyses with SOC as perturbation within the LS coupling scheme. The observed spin orientations of Sr3NiIrO6 and Sr2IrO4 are correctly predicted by DFT calculations, and are accounted for by the perturbation theory analysis. As for the spin orientation of Na2IrO3,more » both experimental studies and DFT calculations have not been unequivocal. Our analysis reveals that the Ir4+ spin orientation of Na2IrO3 should have nonzero components along the c- and a-axes directions. The spin orientations determined by DFT calculations are sensitive to the accuracy of the crystal structures employed, which is explained by perturbation theory analyses when interactions between adjacent Ir4+ ions are taken into consideration. There are indications implying that the 5d electrons of Na2IrO3 are less strongly localized compared with those of Sr3NiIrO6 and Sr2IrO4. This implication was confirmed by showing that the Madelung potentials of the Ir4+ ions are less negative in Na2IrO3 than in Sr3NiIrO6, Sr2IrO4. Most transition-metal S = 1/2 ions do have magnetic anisotropies because the SOC induces interactions among their crystal-field split d-states, and the associated mixing of the states modifies only the orbital parts of the states. This finding cannot be mimicked by a spin Hamiltonian because this model Hamiltonian lacks the orbital degree of freedom, thereby leading to the spin-half syndrome. As a result, the spin-orbital entanglement for the 5d spin-half ions Ir4+ is not as strong as has been assumed lately.« less
Eich, F. G.; Hellgren, Maria
2014-12-14
We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this purpose, we construct the most simple meta-GGA by expressing the local exchange-correlation energy per particle as a function of a fictitious density, which is obtained by inverting the Thomas-Fermi kinetic-energy functional. This simple functional considerably improves the total energy of atoms as compared to the standard local density approximation. The corresponding exchange-correlation potentials are then determined exactly through a solution of the optimized effective potential equation. These potentials support an additional bound state and exhibit a derivative discontinuity at integer particle numbers. We further demonstrate that through the kinetic-energy density any meta-GGA incorporates a derivative discontinuity. However, we also find that for commonly used meta-GGAs the discontinuity is largely underestimated and in some cases even negative.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Benjamin A. Frandsen; Brunelli, Michela; Page, Katharine; Uemura, Yasutomo J.; Staunton, Julie B.; Billinge, Simon J. L.
2016-05-11
Here, we present a temperature-dependent atomic and magnetic pair distribution function (PDF) analysis of neutron total scattering measurements of antiferromagnetic MnO, an archetypal strongly correlated transition-metal oxide. The known antiferromagnetic ground-state structure fits the low-temperature data closely with refined parameters that agree with conventional techniques, confirming the reliability of the newly developed magnetic PDF method. The measurements performed in the paramagnetic phase reveal significant short-range magnetic correlations on a ~1 nm length scale that differ substantially from the low-temperature long-range spin arrangement. Ab initio calculations using a self-interaction-corrected local spin density approximation of density functional theory predict magnetic interactions dominatedmore » by Anderson superexchange and reproduce the measured short-range magnetic correlations to a high degree of accuracy. Further calculations simulating an additional contribution from a direct exchange interaction show much worse agreement with the data. Furthermore, the Anderson superexchange model for MnO is thus verified by experimentation and confirmed by ab initio theory.« less
Xianlong, Gao; Polini, Marco; Tosi, M. P.; Campo, Vivaldo L. Jr.; Capelle, Klaus; Rigol, Marcos
2006-04-15
We present an extensive numerical study of the ground-state properties of confined repulsively interacting fermions in one-dimensional optical lattices. Detailed predictions for the atom-density profiles are obtained from parallel Kohn-Sham density-functional calculations and quantum Monte Carlo simulations. The density-functional calculations employ a Bethe ansatz based local-density approximation for the correlation energy that accounts for Luttinger-liquid and Mott-insulator physics. Semianalytical and fully numerical formulations of this approximation are compared with each other and with a cruder Thomas-Fermi-type local-density approximation for the total energy. Precise quantum Monte Carlo simulations are used to assess the reliability of the various local-density approximations, and in conjunction with these provide a detailed microscopic picture of the consequences of the interplay between particle-particle interactions and confinement in one-dimensional systems of strongly correlated fermions.
Kraisler, Eli; Kronik, Leeor
2014-05-14
The fundamental gap is a central quantity in the electronic structure of matter. Unfortunately, the fundamental gap is not generally equal to the Kohn-Sham gap of density functional theory (DFT), even in principle. The two gaps differ precisely by the derivative discontinuity, namely, an abrupt change in slope of the exchange-correlation energy as a function of electron number, expected across an integer-electron point. Popular approximate functionals are thought to be devoid of a derivative discontinuity, strongly compromising their performance for prediction of spectroscopic properties. Here we show that, in fact, all exchange-correlation functionals possess a derivative discontinuity, which arises naturally from the application of ensemble considerations within DFT, without any empiricism. This derivative discontinuity can be expressed in closed form using only quantities obtained in the course of a standard DFT calculation of the neutral system. For small, finite systems, addition of this derivative discontinuity indeed results in a greatly improved prediction for the fundamental gap, even when based on the most simple approximate exchange-correlation density functional the local density approximation (LDA). For solids, the same scheme is exact in principle, but when applied to LDA it results in a vanishing derivative discontinuity correction. This failure is shown to be directly related to the failure of LDA in predicting fundamental gaps from total energy differences in extended systems.
Complex-energy approach to sum rules within nuclear density functional theory
Hinohara, Nobuo; Kortelainen, Markus; Nazarewicz, Witold; Olsen, Erik
2015-04-27
The linear response of the nucleus to an external field contains unique information about the effective interaction, correlations governing the behavior of the many-body system, and properties of its excited states. To characterize the response, it is useful to use its energy-weighted moments, or sum rules. By comparing computed sum rules with experimental values, the information content of the response can be utilized in the optimization process of the nuclear Hamiltonian or nuclear energy density functional (EDF). But the additional information comes at a price: compared to the ground state, computation of excited states is more demanding. To establish an efficient framework to compute energy-weighted sum rules of the response that is adaptable to the optimization of the nuclear EDF and large-scale surveys of collective strength, we have developed a new technique within the complex-energy finite-amplitude method (FAM) based on the quasiparticle random- phase approximation. The proposed sum-rule technique based on the complex-energy FAM is a tool of choice when optimizing effective interactions or energy functionals. The method is very efficient and well-adaptable to parallel computing. As a result, the FAM formulation is especially useful when standard theorems based on commutation relations involving the nuclear Hamiltonian and external field cannot be used.
Complex-energy approach to sum rules within nuclear density functional theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Hinohara, Nobuo; Kortelainen, Markus; Nazarewicz, Witold; Olsen, Erik
2015-04-27
The linear response of the nucleus to an external field contains unique information about the effective interaction, correlations governing the behavior of the many-body system, and properties of its excited states. To characterize the response, it is useful to use its energy-weighted moments, or sum rules. By comparing computed sum rules with experimental values, the information content of the response can be utilized in the optimization process of the nuclear Hamiltonian or nuclear energy density functional (EDF). But the additional information comes at a price: compared to the ground state, computation of excited states is more demanding. To establish anmore » efficient framework to compute energy-weighted sum rules of the response that is adaptable to the optimization of the nuclear EDF and large-scale surveys of collective strength, we have developed a new technique within the complex-energy finite-amplitude method (FAM) based on the quasiparticle random- phase approximation. The proposed sum-rule technique based on the complex-energy FAM is a tool of choice when optimizing effective interactions or energy functionals. The method is very efficient and well-adaptable to parallel computing. As a result, the FAM formulation is especially useful when standard theorems based on commutation relations involving the nuclear Hamiltonian and external field cannot be used.« less
Chakraborty, Brahmananda Ramaniah, Lavanya M.
2014-04-24
Transition metal - free - ferromagnetism in diluted magnetic semiconductors (DMS) is of much current interest in the search for more efficient DMS materials for spintronic applications. Here, we report the results of our first principles density functional theory (DFT) study on impurity - induced ferromagnetism in non-magnetic SnO{sub 2} by a non-magnetic impurity. The impurities considered are sp-type of group 1A and 2A elements X (X = Li, Na, K, Be, Mg, Ca). Even a single atom of the group 1A elements makes the system magnetic, whereas for the group 2A elements Ca and Mg, a higher doping is required to induce ferromagnetism. For all the elements studied, the magnetic moment appears to increase with the doping concentration, at least at certain impurity separations, which is a positive indicator for practical applications.
Veals, Jeffrey D.; Thompson, Donald L.
2014-04-21
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by NN and CN bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by NN bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by CN bond fission.
Lykissa, Iliana; Li, Shu-Yi; Granqvist, Claes G.; Niklasson, Gunnar A.; Ramzan, Muhammad; Chakraborty, Sudip; Ahuja, Rajeev
2014-05-14
Thin films of V{sub 2}O{sub 5} were prepared by sputter deposition onto transparent and electrically conducting substrates and were found to be X-ray amorphous. Their electrochemical density of states was determined by chronopotentiometry and displayed a pronounced low-energy peak followed by an almost featureless contribution at higher energies. These results were compared with density functional theory calculations for amorphous V{sub 2}O{sub 5}. Significant similarities were found between measured data and computations; specifically, the experimental low-energy peak corresponds to a split-off part of the conduction band apparent in the computations. Furthermore, the calculations approximately reproduce the experimental band gap observed in optical measurements.
Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; Nenoff, Tina M.
2015-03-02
Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M_{2}(dobdc) and M_{3}(btc)_{2}. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trend in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.
Vijayakumar, M.; Hu, Jian Z.
2013-10-15
To analyze the lithium ion interaction with realistic graphene surfaces, we carried out dispersion corrected DFT-D3 studies on graphene with common point defects and chemisorbed oxygen containing functional groups along with defect free graphene surface. Our study reveals that, the interaction between lithium ion (Li+) and graphene is mainly through the delocalized π electron of pure graphene layer. However, the oxygen containing functional groups pose high adsorption energy for lithium ion due to the Li-O ionic bond formation. Similarly, the point defect groups interact with lithium ion through possible carbon dangling bonds and/or cation-π type interactions. Overall these defect sites render a preferential site for lithium ions compared with pure graphene layer. Based on these findings, the role of graphene surface defects in lithium battery performance were discussed.
Morzan, Uriel N.; Ramrez, Francisco F.; Scherlis, Damin A. E-mail: mcgl@qb.ffyb.uba.ar; Lebrero, Mariano C. Gonzlez E-mail: mcgl@qb.ffyb.uba.ar
2014-04-28
This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrixrequired to propagate the electron dynamics, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.
Successes and failures of Hubbard-corrected density functional theory. The case of Mg doped LiCoO2
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Santana Palacio, Juan A.; Kim, Jeongnim; Kent, Paul R.; Reboredo, Fernando A.
2014-10-28
We have evaluated the successes and failures of the Hubbard-corrected density functional theory approach to study Mg doping of LiCoO2. We computed the effect of the U parameter on the energetic, geometric, and electronic properties of two possible doping mechanisms: (1) substitution of Mg onto a Co (or Li) site with an associated impurity state and (2) formation of impurity-state-free complexes of substitutional Mg and point defects in LiCoO2. We find that formation of impurity states results in changes on the valency of Co in LiCoO2. Variation of the Co U shifts the energy of the impurity state, resulting inmore » energetic, geometric, and electronic properties that depend significantly on the specific value of U. In contrast, the properties of the impurity-state-free complexes are insensitive to U. These results identify reasons for the strong dependence on the doping properties on the chosen value of U and for the overall difficulty of achieving agreement with the experimentally known energetic and electronic properties of doped transition metal oxides such as LiCoO2.« less
Walsh, Aron; Wei, S.-H.; Yan Yanfa; Al-Jassim, M. M.; Turner, John A.; Woodhouse, Michael; Parkinson, B. A.
2007-10-15
A systematic study of nine binary and ternary spinel oxides formed from Co, Al, and Fe is presented by means of density functional theory. Analysis of the structural, magnetic, and electronic properties through the series of materials is carried out. Preference for the octahedral spinel sites are found in the order Fe
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Rudin, Sven P.; Johnson, David C.
2015-04-30
Among composite materials that layer constituent substances of nanoscale thicknesses, [(SnSe)1+y ]m(VSe2)n emerges as an example where the constituents retain incommensurate lattice structures. Perpendicular to the stacking direction, the system exhibits random translations and random rotations on average, i.e., turbostratic disorder, with local regions showing twelvefold diffraction patterns. Earlier theoretical work on these structures showed that combining density functional theory with an empirical treatment of the van der Waals interaction gave structural parameters in good agreement with experiment, but no attempt was made to examine the relative orientations. Here we approximate the extended system with one extended constituent and onemore » finite constituent, which allows the treatment of all relative orientations on equal footing. Furthermore, the calculations show how the twelvefold periodicity follows from how the ions of the SnSe layer lock in with favored positions relative to the VSe2 layer, and the associated energy scale supports arguments for the overall turbostratic disorder.« less
Hydroxide Degradation Pathways for Substituted Benzyltrimethyl Ammonium: A DFT Study
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Long, Hai; Pivovar, Bryan S.
2014-11-01
The stability of cations used in the alkaline exchange membranes has been a major challenge. In this paper, degradation energy barriers were investigated by density functional theory for substituted benzyltrimethyl ammonium (BTMA+) cations. Findings show that electron-donating substituent groups at meta-position(s) of the benzyl ring could result in increased degradation barriers. However, after investigating more than thirty substituted BTMA+ cations, the largest improvement in degradation barrier found was only 6.7 kJ/mol. This suggests a modest (8×) improvement in stability for this type of approach may be possible, but for anything greater other approaches will need to be pursued.
Ohashi, Kazuhiko Sekiya, Hiroshi; Sasaki, Jun; Yamamoto, Gun; Judai, Ken; Nishi, Nobuyuki
2014-12-07
Hydrated Fe{sup +} ions are produced in a laser-vaporization cluster source of a triple quadrupole mass spectrometer. The Fe{sup +}(H{sub 2}O){sub n} (n = 3–8) complexes are mass-selected and probed with infrared (IR) photodissociation spectroscopy in the OH-stretch region. Density functional theory (DFT) calculations are also carried out for analyzing the experimental IR spectra and for evaluating thermodynamic quantities of low-lying isomers. Solvation through H-bonding instead of direct coordination to Fe{sup +} is observed already at n = 3, indicating the completion of the first hydration shell with two H{sub 2}O molecules. Size dependent variations in the spectra for n = 5–7 provide evidence for the second-shell completion at n = 6, where a linearly coordinated Fe{sup +}(H{sub 2}O){sub 2} subunit is solvated with four H{sub 2}O molecules. Overall spectral features for n = 3–8 agree well with those predicted for 2-coordinated structures. DFT calculations predict that such 2-coordinated structures are lowest in energy for smaller n. However, 4-coordinated isomers are predicted to be more stable for n = 7 and 8; the energy ordering is in conflict with the IR spectroscopic observation. Examination of free energy as a function of temperature suggests that the ordering of the isomers at warmer temperatures can be different from the ordering near 0 K. For n = 7 and 8, the 4-coordinated isomers should be observed at low temperatures because they are lowest in enthalpy. Meanwhile, outer-shell waters in the 2-coordinated structures are bound less rigidly; their contribution to entropy is rather large. The 2-coordinated structures become abundant at warmer temperatures, owing to the entropy effect.
Khaliullin, Rustam Z.; Bell, Alexis T.
2002-09-05
Density functional theory was used to investigate the mechanism and kinetics of methanol oxidation to formaldehyde over vanadia supported on silica, titania, and zirconia. The catalytically active site was modeled as an isolated VO{sub 4} unit attached to the support. The calculated geometry and vibrational frequencies of the active site are in good agreement with experimental measurements both for model compounds and oxide-supported vanadia. Methanol adsorption is found to occur preferentially with the rupture of a V-O-M bond (M = Si, Ti, Zr) and with preferential attachment of a methoxy group to V. The vibrational frequencies of the methoxy group are in good agreement with those observed experimentally as are the calculated isobars. The formation of formaldehyde is assumed to occur via the transfer of an H atom of a methoxy group to the O atom of the V=O group. The activation energy for this process is found to be in the range of 199-214 kJ/mol and apparent activation energies for the overall oxidation of methanol to formaldehyde are predicted to lie in the range of 112-123 kJ/mol, which is significantly higher than that found experimentally. Moreover, the predicted turnover frequency (TOF) for methanol oxidation is found to be essentially independent of support composition, whereas experiments show that the TOF is 10{sup 3} greater for titania- and zirconia-supported vanadia than for silica-supported vanadia. Based on these findings, it is proposed that the formation of formaldehyde from methoxy groups may require pairs of adjacent VO{sub 4} groups or V{sub 2}O{sub 7} dimer structures.
Optimized nested Markov chain Monte Carlo sampling: theory
Coe, Joshua D; Shaw, M Sam; Sewell, Thomas D
2009-01-01
Metropolis Monte Carlo sampling of a reference potential is used to build a Markov chain in the isothermal-isobaric ensemble. At the endpoints of the chain, the energy is reevaluated at a different level of approximation (the 'full' energy) and a composite move encompassing all of the intervening steps is accepted on the basis of a modified Metropolis criterion. By manipulating the thermodynamic variables characterizing the reference system we maximize the average acceptance probability of composite moves, lengthening significantly the random walk made between consecutive evaluations of the full energy at a fixed acceptance probability. This provides maximally decorrelated samples of the full potential, thereby lowering the total number required to build ensemble averages of a given variance. The efficiency of the method is illustrated using model potentials appropriate to molecular fluids at high pressure. Implications for ab initio or density functional theory (DFT) treatment are discussed.
Long, Run; English, Niall J.
2011-04-04
The electronic structures of Mg/Ca- and/or Mo/W- (mono- and co-) doped anatase TiO{sub 2} have been investigated via generalized Kohn-Sham theory with the Heyd-Scuseria-Ernzerhof hybrid functional for exchange-correlation (J. Heyd et al., [J. Chem. Phys. 118, 8207 (2003)], J. Heyd et al., [J. Chem. Phys. 124, 219906 (2006)], and J. Paier et al., [J. Chem. Phys. 125, 249901 (2006)]), in the context of density functional theory. Gap narrowing is small for monodoping, which also creates impuritiy bands in the ''forbidden gap,'' either as acceptor or donor states, limiting possible utility as visible-light photocatalysts. However, codoping of Mg/Ca and Mo/W not only induces appreciable gap narrowing, but also serves to passivate the impurity bands, which can harvest visible-light to a greater extent. Considering ionic radii, Mg and Mo should constitute the best cation-pair.
Tussupbayev, Samat; Govind, Niranjan; Lopata, Kenneth A.; Cramer, Christopher J.
2015-03-10
We assess the performance of real-time time-dependent density functional theory (RT-TDDFT) for the calculation of absorption spectra of 12 organic dye molecules relevant to photovoltaics and dye sensitized solar cells with 8 exchange-correlation functionals (3 traditional, 3 global hybrids, and 2 range-separated hybrids). We compare the calculations with traditional linear-response (LR) TDDFT. In addition, we demonstrate the efficacy of the RT-TDDFT approach to calculate wide absorption spectra of two large chromophores relevant to photovoltaics and molecular switches.
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... an accelerated density functional theory (DFT)-based computational strategy to determine ... Beginning with periodic DFT calculations on Pt(111), the thermochemistry of glycerol ...
Final Technical Report for DE-SC0001878 [Theory and Simulation of Defects in Oxide Materials
Chelikowsky, James R.
2014-04-14
We explored a wide variety of oxide materials and related problems, including materials at the nanoscale and generic problems associated with oxide materials such as the development of more efficient computational tools to examine these materials. We developed and implemented methods to understand the optical and structural properties of oxides. For ground state properties, our work is predominantly based on pseudopotentials and density functional theory (DFT), including new functionals and going beyond the local density approximation (LDA): LDA+U. To study excited state properties (quasiparticle and optical excitations), we use time dependent density functional theory, the GW approach, and GW plus Bethe-Salpeter equation (GW-BSE) methods based on a many-body Green function approaches. Our work focused on the structural, electronic, optical and magnetic properties of defects (such as oxygen vacancies) in hafnium oxide, titanium oxide (both bulk and clusters) and related materials. We calculated the quasiparticle defect states and charge transition levels of oxygen vacancies in monoclinic hafnia. we presented a milestone G0W0 study of two of the crystalline phases of dye-sensitized TiO{sub 2} clusters. We employed hybrid density functional theory to examine the electronic structure of sexithiophene/ZnO interfaces. To identify the possible effect of epitaxial strain on stabilization of the ferromagnetic state of LaCoO{sub 3} (LCO), we compare the total energy of the magnetic and nonmagnetic states of the strained theoretical bulk structure.
Arghavani Nia, Borhan; Sedighi, Matin; Shahrokhi, Masoud; Moradian, Rostam
2013-11-15
A density functional theory study of structural, electronical and optical properties of Ca{sub 3}Sb{sub 2} compound in hexagonal and cubic phases is presented. In the exchangecorrelation potential, generalized gradient approximation (PBE-GGA) has been used to calculate lattice parameters, bulk modulus, cohesive energy, dielectric function and energy loss spectra. The electronic band structure of this compound has been calculated using the above two approximations as well as another form of PBE-GGA, proposed by Engle and Vosko (EV-GGA). It is found that the hexagonal phase of Ca{sub 3}Sb{sub 2} has an indirect gap in the ??N direction; while in the cubic phase there is a direct-gap at the ? point in the PBE-GGA and EV-GGA. Effects of applying pressure on the band structure of the system studied and optical properties of these systems were calculated. - Graphical abstract: A density functional theory study of structural, electronic and optical properties of Ca{sub 3}Sb{sub 2} compound in hexagonal and cubic phases is presented. Display Omitted - Highlights: Physical properties of Ca{sub 3}Sb{sub 2} in hexagonal and cubic phases are investigated. It is found that the hexagonal phase is an indirect gap semiconductor. Ca{sub 3}Sb{sub 2} is a direct-gap semiconductor at the ? point in the cubic phase. By increasing pressure the semiconducting band gap and anti-symmetry gap are decreased.
Ribeiro, M.
2015-06-21
Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost.
Afshar, Mahdi; Sargolzaei, Mohsen
2013-11-15
We have demonstrated electronic structure and magnetic properties of Cu{sub 3}, Ag{sub 3} and Au{sub 3} trimers using a full potential local orbital method in the framework of relativistic density functional theory. We have also shown that the non-relativistic generalized gradient approximation for the exchange-correlation energy functional gives reliable magnetic properties in coinage metal trimers compared to experiment. In addition we have indicated that the spin-orbit coupling changes the structure and magnetic properties of gold trimer while the structure and magnetic properties of copper and silver trimers are marginally affected. A significant orbital moment of 0.21?{sub B} was found for most stable geometry of the gold trimer whereas orbital magnetism is almost quenched in the copper and silver trimers.
Fahleson, Tobias; Norman, Patrick; Coriani, Sonia; Rizzo, Antonio; Rikken, Geert L. J. A.
2013-11-21
We report on the results of a systematic ab initio study of the Jones birefringence of noble gases, of furan homologues, and of monosubstituted benzenes, in the gas phase, with the aim of analyzing the behavior and the trends within a list of systems of varying size and complexity, and of identifying candidates for a combined experimental/theoretical study of the effect. We resort here to analytic linear and nonlinear response functions in the framework of time-dependent density functional theory. A correlation is made between the observable (the Jones constant) and the atomic radius for noble gases, or the permanent electric dipole and a structure/chemical reactivity descriptor as the para Hammett constant for substituted benzenes.
Li, Xiaozhou; Bond, Andrew D.; Johansson, Kristoffer E.; Van de Streek, Jacco
2014-08-01
The crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide contains an imine tautomer, rather than the previously reported amine tautomer. The tautomers can be distinguished using dispersion-corrected density functional theory calculations and by comparison of calculated and measured {sup 13}C solid-state NMR spectra. The crystal structure of the title compound, C{sub 11}H{sub 13}N{sub 3}O{sub 2}S{sub 2}, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated {sup 13}C solid-state NMR spectra [Hangan et al. (2010 ▶). Acta Cryst. B66, 615–621]. The mol@@ecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thia@@diazol-2-yl)-p-toluene@@sulfonamide], rather than the correct imine tautomer. The protonation site on the mol@@ecule’s 1,3,4-thia@@diazole ring is indicated by the inter@@molecular contacts in the crystal structure: N—H⋯O hydrogen bonds are established at the correct site, while the alternative protonation site does not establish any notable inter molecular inter@@actions. The two tautomers provide essentially identical Rietveld fits to laboratory PXRD data, and therefore they cannot be directly distinguished in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported qu@@anti@@tative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation of the {sup 13}C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured {sup 13}C SS-NMR spectrum.
Aquino, Fredy W.; Govind, Niranjan; Autschbach, Jochen
2011-10-01
Density functional theory (DFT) calculations of NMR chemical shifts and molecular g-tensors with Gaussian-type orbitals are implemented via second-order energy derivatives within the scalar relativistic zeroth order regular approximation (ZORA) framework. Nonhybrid functionals, standard (global) hybrids, and range-separated (Coulomb-attenuated, long-range corrected) hybrid functionals are tested. Origin invariance of the results is ensured by use of gauge-including atomic orbital (GIAO) basis functions. The new implementation in the NWChem quantum chemistry package is verified by calculations of nuclear shielding constants for the heavy atoms in HX (X=F, Cl, Br, I, At) and H2X (X = O, S, Se, Te, Po), and Te chemical shifts in a number of tellurium compounds. The basis set and functional dependence of g-shifts is investigated for 14 radicals with light and heavy atoms. The problem of accurately predicting F NMR shielding in UF6-nCln, n = 1 to 6, is revisited. The results are sensitive to approximations in the density functionals, indicating a delicate balance of DFT self-interaction vs. correlation. For the uranium halides, the results with the range-separated functionals are mixed.
Cox, Stephen J.; Michaelides, Angelos; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ ; Towler, Michael D.; Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, J.J. Thomson Avenue, Cambridge CB3 0HE ; Alf, Dario; Department of Earth Sciences, University College London Gower Street, London WC1E 6BT
2014-05-07
High quality reference data from diffusion Monte Carlo calculations are presented for bulk sI methane hydrate, a complex crystal exhibiting both hydrogen-bond and dispersion dominated interactions. The performance of some commonly used exchange-correlation functionals and all-atom point charge force fields is evaluated. Our results show that none of the exchange-correlation functionals tested are sufficient to describe both the energetics and the structure of methane hydrate accurately, while the point charge force fields perform badly in their description of the cohesive energy but fair well for the dissociation energetics. By comparing to ice I{sub h}, we show that a good prediction of the volume and cohesive energies for the hydrate relies primarily on an accurate description of the hydrogen bonded water framework, but that to correctly predict stability of the hydrate with respect to dissociation to ice I{sub h} and methane gas, accuracy in the water-methane interaction is also required. Our results highlight the difficulty that density functional theory faces in describing both the hydrogen bonded water framework and the dispersion bound methane.
Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan
2015-11-09
Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.
Daene, Markus; Kim, Soo Kyung; Surh, Michael P.; Aberg, Daniel; Benedict, Lorin X.
2015-06-15
We present and discuss density functional theory calculations of magnetic properties of the family of ferromagnetic compounds, (Fe_{1-x}Co_{x})_{2}B, focusing specifically on the magnetocrystalline anisotropy energy (MAE). Using periodic supercells of various sizes (up to 96 atoms), it is shown that the general qualitative features of the composition dependence of the MAE is in agreement with experimental findings, while our predicted magnitudes are larger than those of experiment. We find that the use of small supercells (6 and 12-atom) favors larger MAE values relative to a statistical sample of configurations constructed with 96-atom supercells. As a result, the effect of lattice relaxations is shown to be small. Calculations of the Curie temperature for this alloy are also presented.
Kawaguchi, Yoshizo; Sasaki, Fumio; Mochizuki, Hiroyuki; Ishitsuka, Tomoaki; Tomie, Toshihisa; Ootsuka, Teruhisa; Watanabe, Shuji; Shimoi, Yukihiro; Yamao, Takeshi; Hotta, Shu
2013-02-28
We have investigated electronic states in the valence electron bands for the thin films of three thiophene/phenylene co-oligomer (TPCO) compounds, 2,5-bis(4-biphenylyl)thiophene (BP1T), 1,4-bis(5-phenylthiophen-2-yl)benzene (AC5), and 1,4-bis{l_brace}5-[4-(trifluoromethyl)phenyl]thiophen-2-yl{r_brace}benzene (AC5-CF{sub 3}), by using extreme-UV excited photoelectron spectroscopy (EUPS). By comparing both EUPS spectra and secondary electron spectra between AC5 and AC5-CF{sub 3}, we confirm that CF{sub 3} substitution to AC5 deepens valence states by 2 eV, and increases the ionization energy by 3 eV. From the cut-off positions of secondary electron spectra, the work functions of AC5, AC5-CF{sub 3}, and BP1T are evaluated to be 3.8 eV, 4.8 eV, and 4.0 eV, respectively. We calculate molecular orbital (MO) energy levels by the density functional theory and compare results of calculations with those of experiments. Densities of states obtained by broadening MO levels well explain the overall features of experimental EUPS spectra of three TPCOs.
Kuiken, Benjamin E. Van; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira
2013-04-26
Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.
Density-functional Monte-Carlo simulation of CuZn order-disorder transition
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Khan, Suffian N.; Eisenbach, Markus
2016-01-25
We perform a Wang-Landau Monte Carlo simulation of a Cu0.5Zn0.5 order-disorder transition using 250 atoms and pairwise atom swaps inside a 5 x 5 x 5 BCC supercell. Each time step uses energies calculated from density functional theory (DFT) via the all-electron Korringa-Kohn- Rostoker method and self-consistent potentials. Here we find CuZn undergoes a transition from a disordered A2 to an ordered B2 structure, as observed in experiment. Our calculated transition temperature is near 870 K, comparing favorably to the known experimental peak at 750 K. We also plot the entropy, temperature, specific-heat, and short-range order as a function ofmore » internal energy.« less
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Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC) Energy Frontier ... science, molecular dynamics (MD), density functional theory (DFT), quantum ...
Wang, Chen-Guang; Huang, Kai E-mail: wji@ruc.edu.cn; Ji, Wei E-mail: wji@ruc.edu.cn
2014-11-07
During the dissociative adsorption on a solid surface, the substrate usually participates in a passive manner to accommodate fragments produced upon the cleavage of the internal bond(s) of a (transient) molecular adsorbate. This simple picture, however, neglects the flexibility of surface atoms. Here, we report a Density Functional Theory study to revisit our early studies of the dissociative adsorption of CH{sub 3}X (X = Br and Cl) on Si(100). We have identified a new reaction pathway, which involves a flip of a silicon dimer; this new pathway agrees better with experiments. For our main exemplar of CH{sub 3}Br, insights have been gained using a simple model that involves a three-atom reactive center, Br-C-Si. When the silicon dimer flips, the interaction between C and Si in the Br-C-Si center is enhanced, evident in the increased energy-split of the frontier orbitals. We also examine how the dissociation dynamics of CH{sub 3}Br is altered on a heterodimer (Si-Al, Si-P, and Si-Ge) in a Si(100) surface. In each case, we conclude, on the basis of computed reaction pathways, that no heterodimer flipping is involved before the system transverses the transition state to dissociative adsorption.
Minezawa, Noriyuki
2014-10-28
Examining photochemical processes in solution requires understanding the solvent effects on the potential energy profiles near conical intersections (CIs). For that purpose, the CI point in solution is determined as the crossing between nonequilibrium free energy surfaces. In this work, the nonequilibrium free energy is described using the combined method of linear-response free energy and collinear spin-flip time-dependent density functional theory. The proposed approach reveals the solvent effects on the CI geometries of stilbene in an acetonitrile solution and those of thymine in water. Polar acetonitrile decreases the energy difference between the twisted minimum and twisted-pyramidalized CI of stilbene. For thymine in water, the hydrogen bond formation stabilizes significantly the CI puckered at the carbonyl carbon atom. The result is consistent with the recent simulation showing that the reaction path via this geometry is open in water. Therefore, the present method is a promising way of identifying the free-energy crossing points that play an essential role in photochemistry of solvated molecules.
Baer, Marcel D.; Kuo, I-F W.; Tobias, Douglas J.; Mundy, Christopher J.
2014-07-17
The propensities of the water self ions, H3O+ and OH- , for the air-water interface has implications for interfacial acid-base chemistry. Despite numerous experimental and computational studies, no consensus has been reached on the question of whether or not H3O+ and/or OH- prefer to be at the water surface or in the bulk. Here we report a molecular dynamics simulation study of the bulk vs. interfacial behavior of H3O+ and OH- that employs forces derived from density functional theory with a generalized gradient approximation exchangecorrelation functional (specifically, BLYP) and empirical dispersion corrections. We computed the potential of mean force (PMF) for H3O+ as a function of the position of the ion in a 215-molecule water slab. The PMF is flat, suggesting that H3O+ has equal propensity for the air-water interface and the bulk. We compare the PMF for H3O+ to our previously computed PMF for OH- adsorption, which contains a shallow minimum at the interface, and we explore how differences in solvation of each ion at the interface vs. the bulk are connected with interfacial propensity. We find that the solvation shell of H3O+ is only slightly dependent on its position in the water slab, while OH- partially desolvates as it approaches the interface, and we examine how this difference in solvation behavior is manifested in the electronic structure and chemistry of the two ions. DJT was supported by National Science Foundation grant CHE-0909227. CJM was supported by the U.S. Department of Energy‘s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the Department of Energy by Battelle. The potential of mean force required resources of the Oak Ridge Leadership Computing Facility at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DEAC05-00OR22725. The remaining simulations and analysis used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. at at Lawrence Berkeley National Laboratory. MDB is grateful for the support of the Linus Pauling Distinguished Postdoctoral Fellowship Program at PNNL.
Al-Hamdani, Yasmine S.; Alf, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos
2014-10-22
Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B?N?H?) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.
Boereboom, J. M.; Wijzenbroek, M.; Somers, M. F.; Kroes, G. J.
2013-12-28
Recently, an implementation of the specific reaction parameter (SRP) approach to density functional theory (DFT) was used to study several reactive scattering experiments of H{sub 2} on Cu(111). It was possible to obtain chemical accuracy (1 kcal/mol ? 4.2 kJ/mol), and therefore, accurately model this paradigmatic example of activated H{sub 2} dissociation on a metal surface. In this work, the SRP-DFT methodology is applied to the dissociation of hydrogen on a Pd(111) surface, in order to test whether the SRP-DFT approach is also applicable to non-activated H{sub 2}-metal systems. In the calculations, the BornOppenheimer static surface approximations are used. A comparison to molecular beam sticking experiments, performed at incidence energies ?125 meV, on H{sub 2} + Pd(111) suggested the PBE-vdW [where the Perdew, Burke, and Ernzerhof (PBE) correlation is replaced by van der Waals correlation] functional as a candidate SRP density functional describing the reactive scattering of H{sub 2} on Pd(111). Unfortunately, quantum dynamics calculations are not able to reproduce the molecular beam sticking results for incidence energies <125 meV. From a comparison to initial state-resolved (degeneracy averaged) sticking probabilities it seems clear that for H{sub 2} + Pd(111) dynamic trapping and steering effects are important, and that these effects are not yet well modeled with the potential energy surfaces considered here. Applying the SRP-DFT method to systems where H{sub 2} dissociation is non-activated remains difficult. It is suggested that a density functional that yields a broader barrier distribution and has more non-activated pathways than PBE-vdW (i.e., non-activated dissociation at some sites but similarly high barriers at the high energy end of the spectrum) should allow a more accurate description of the available experiments. Finally, it is suggested that new and better characterized molecular beam sticking experiments be done on H{sub 2} + Pd(111), to facilitate the development of a more accurate theoretical description of this system.
Functionalization of multi-walled carbon nanotubes using water-assisted chemical vapor deposition
Ran Maofei; Sun Wenjing; Liu Yan; Chu Wei; Jiang Chengfa
2013-01-15
A simple and novel method, water-assisted chemical vapor deposition (CVD) was developed to functionalize multi-walled carbon nanotubes (MWCNTs) during the synthesis process. The functionalized MWCNTs were characterized using Raman spectroscopy, XPS, TGA, NH{sub 3}-TPD, SEM and HR-TEM. It was found that new defects are introduced and the amount of acidic groups is increased on the MWCNT surface during the water-assisted CVD process. The amount of C-OH and C-O group on the MWCNT surface is found to be increased from 21.1% to 42% with water vapor assistance. Density functional theory (DFT) was employed to study the chemical behavior of water vapor molecule on the catalyst particle surface of Ni(1 1 1) cluster. Based on the experimental and DFT simulation results, a mechanism for functionalization of MWCNTs by water-assisted CVD is proposed. - Graphical abstract: Water is adsorbed and activated on Ni surface, then dissociated into OH and O species, followed by part of OH and O species desorbed from the surface. Finally, the desorbed OH and O species oxidize the unsaturated carbon atoms of carbon nanotubes, form defects and oxygen-containing groups. Highlights: Black-Right-Pointing-Pointer MWCNTs were functionalized by water-assisted CVD method. Black-Right-Pointing-Pointer Defects and weak-medium acidic sites were created on the MWCNT sidewalls. Black-Right-Pointing-Pointer Oxygen-containing groups in functionalized MWCNT were increased from 21.1% to 42%. Black-Right-Pointing-Pointer A mechanism for the influence of water vapor on MWCNTs was proposed.
Yan, Li-Li; Liu, Yi-Rong; Huang, Teng; Jiang, Shuai; Wen, Hui; Gai, Yan-Bo; Zhang, Wei-Jun E-mail: wjzhang@aiofm.ac.cn; Huang, Wei E-mail: wjzhang@aiofm.ac.cn; School of Environmental Science and Optoelectronic Technology, University of Science and Technology of China, Hefei, Anhui 230026
2013-12-28
The equilibrium geometric structures, relative stabilities, and electronic properties of Au{sub n}C{sup ?} and Au{sub n+1}{sup ?} (n = 110) clusters are systematically investigated using density functional theory with hyper-generalized gradient approximation. The optimized geometries show that one Au atom capped on Au{sub n?1}C{sup ?} clusters is a dominant growth pattern for Au{sub n}C{sup ?} clusters. In contrast to Au{sub n+1}{sup ?} clusters, Au{sub n}C{sup ?} clusters are most stable in a quasi-planar or three-dimensional structure because C doping induces the local non-planarity while the rest of the structure continues to grow in a planar mode, resulting in an overall non-2D configuration. The relative stability calculations show that the impurity C atom can significantly enhance the thermodynamic stability of pure gold clusters. Moreover, the effect of C atom on the Au{sub n}{sup ?} host decreases with the increase of cluster size. The HOMO-LUMO gap curves show that the interaction of the C atom with Au{sub n}{sup ?} clusters improves the chemical stability of pure gold clusters, except for Au{sub 3}{sup ?} and Au{sub 4}{sup ?} clusters. In addition, a natural population analysis shows that the charges in corresponding Au{sub n}C{sup ?} clusters transfer from the Au{sub n}{sup ?} host to the C atom. Meanwhile, a natural electronic configuration analysis also shows that the charges mainly transfer between the 2s and 2p orbitals within the C atom.
Lara-Castells, Mara Pilar de; Mitrushchenkov, Alexander O.; Stoll, Hermann
2015-09-14
A combined density functional (DFT) and incremental post-Hartree-Fock (post-HF) approach, proven earlier to calculate He-surface potential energy surfaces [de Lara-Castells et al., J. Chem. Phys. 141, 151102 (2014)], is applied to describe the van der Waals dominated Ag{sub 2}/graphene interaction. It extends the dispersionless density functional theory developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] by including periodic boundary conditions while the dispersion is parametrized via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. Starting with the elementary cluster unit of the target surface (benzene), continuing through the realistic cluster model (coronene), and ending with the periodic model of the extended system, modern ab initio methodologies for intermolecular interactions as well as state-of-the-art van der Waals-corrected density functional-based approaches are put together both to assess the accuracy of the composite scheme and to better characterize the Ag{sub 2}/graphene interaction. The present work illustrates how the combination of DFT and post-HF perspectives may be efficient to design simple and reliable ab initio-based schemes in extended systems for surface science applications.
Salciccioli, Michael [Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI) and Center for Catalytic Science and Technology (CCST); Yu, Weiting [Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI) and Center for Catalytic Science and Technology (CCST); Barteau, Mark A. [Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI) and Center for Catalytic Science and Technology (CCST); Chen, Jingguang G. [Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI) and Center for Catalytic Science and Technology (CCST); Vlachos, Dionisios G. [Univ. of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation (CCEI) and Center for Catalytic Science and Technology (CCST)
2011-05-25
Understanding and controlling bond-breaking sequences of oxygenates on transition metal catalysts can greatly impact the utilization of biomass feedstocks for fuels and chemicals. The decomposition of ethylene glycol, as the simplest representative of biomass-derived polyols, was studied via density functional theory (DFT) calculations to identify the differences in reaction pathways between Pt and the more active Ni/Pt bimetallic catalyst. Comparison of the computed transition states indicated three potentially feasible paths from ethylene glycol to C1 oxygenated adsorbates on Pt. While not important on Pt, the pathway to 1,2-dioxyethylene (OCH?CH?O) is favored energetically on the Ni/Pt catalyst. Temperature-programmed desorption (TPD) experiments were conducted with deuterated ethylene glycols for comparison with DFT results. These experiments confirmed that decomposition of ethylene glycol on Pt proceeds via initial OH bond cleavage, followed by CH and the second OH bond cleavages, whereas on the Ni/Pt surface, both OH bonds are cleaved initially. The results are consistent with vibrational spectra and indicate that tuning of the catalyst surface can selectively control bond breaking. Finally, the significant mechanistic differences in decomposition of polyols compared to that of monoalcohols and hydrocarbons serve to identify general trends in bond scission sequences.
DFT STUDY REVISES INTERSTITIAL CONFIGURATIONS IN HCP Zr
Samolyuk, German D; Golubov, Stanislav I; Osetskiy, Yury N; Stoller, Roger E
2012-06-01
Analysis of experimental result on microstructure evolution in irradiated Zr and alloys has demonstrated that available knowledge on self-interstitial defects in Zr is in contradiction. We therefore have initiated an extensive theoretical and modeling program to clarify this issue. In this report we present first ab initio calculations results of single SIA configurations in Zr. We demonstrate importance of simulations cell size, applied exchange-correlation functional and simulated c/a ratio. The results obtained demonstrate clearly that the most stable configurations are in basal plane and provide some evidences for enhanced interstitial transport along basal planes. The results obtained will be used in generation a new interatomic potential for Zr to be used in large-scale atomistic modeling of mechanisms relevant for radiation-induced microstructure evolution.
DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers
Shirani, Hossein; Jameh-Bozorghi, Saeed; Yousefi, Ali
2015-01-22
In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMOLUMO gaps and NICS values of these compounds have been calculated and analyzed.
DFT study on cysteine adsorption mechanism on Au(111) and Au(110)
Buimaga-Iarinca, Luiza; Floare, Calin G.; Calborean, Adrian; Turcu, Ioan
2013-11-13
Periodic density functional theory calculations were used to investigate relevant aspects of adsorption mechanisms of cysteine dimers in protonated form on Au(111) and Au(110) surfaces. The projected densities of states are explicitly discussed for all main chemical groups of cysteine, i.e. the amino group (NH2), the thiol group (SH) and the carboxylic group (COOH) to identify differences in adsorption mechanism. Special emphasis is put on the analysis of changes in the electronic structure of molecules adsorbed on Au(111) and Au(110) surfaces as well as the accompanying charge transfer mechanisms at molecule-substrate interaction.
Kaufman-Osborn, Tobin; Chagarov, Evgueni A.; Kummel, Andrew C.
2014-05-28
Passivation, functionalization, and atomic layer deposition nucleation via H{sub 2}O{sub 2}(g) and trimethylaluminum (TMA) dosing was studied on the clean Ge(100) surface at the atomic level using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Chemical analysis of the surface was performed using x-ray photoelectron spectroscopy, while the bonding of the precursors to the substrate was modeled with density functional theory (DFT). At room temperature, a saturation dose of H{sub 2}O{sub 2}(g) produces a monolayer of a mixture of OH or O species bonded to the surface. STS confirms that H{sub 2}O{sub 2}(g) dosing eliminates half-filled dangling bonds on the clean Ge(100) surface. Saturation of the H{sub 2}O{sub 2}(g) dosed Ge(100) surface with TMA followed by a 200?C anneal produces an ordered monolayer of thermally stable GeOAl bonds. DFT models and STM simulations provide a consistent model of the bonding configuration of the H{sub 2}O{sub 2}(g) and TMA dosed surfaces. STS verifies the TMA/H{sub 2}O{sub 2}/Ge surface has an unpinned Fermi level with no states in the bandgap demonstrating the ability of a GeOAl monolayer to serve as an ideal template for further high-k deposition.
Rate Theory Modeling and Simulations of Silicide Fuel at LWR Conditions
Miao, Yinbin; Ye, Bei; Mei, Zhigang; Hofman, Gerard; Yacout, Abdellatif
2015-12-10
Uranium silicide (U_{3}Si_{2}) fuel has higher thermal conductivity and higher uranium density, making it a promising candidate for the accident-tolerant fuel (ATF) used in light water reactors (LWRs). However, previous studies on the fuel performance of U_{3}Si_{2}, including both experimental and computational approaches, have been focusing on the irradiation conditions in research reactors, which usually involve low operation temperatures and high fuel burnups. Thus, it is important to examine the fuel performance of U_{3}Si_{2} at typical LWR conditions so as to evaluate the feasibility of replacing conventional uranium dioxide fuel with this silicide fuel material. As in-reactor irradiation experiments involve significant time and financial cost, it is appropriate to utilize modeling tools to estimate the behavior of U_{3}Si_{2} in LWRs based on all those available research reactor experimental references and state-of-the-art density functional theory (DFT) calculation capabilities at the early development stage. Hence, in this report, a comprehensive investigation of the fission gas swelling behavior of U_{3}Si_{2} at LWR conditions is introduced. The modeling efforts mentioned in this report was based on the rate theory (RT) model of fission gas bubble evolution that has been successfully applied for a variety of fuel materials at devious reactor conditions. Both existing experimental data and DFT-calculated results were used for the optimization of the parameters adopted by the RT model. Meanwhile, the fuel-cladding interaction was captured by the coupling of the RT model with simplified mechanical correlations. Therefore, the swelling behavior of U_{3}Si_{2} fuel and its consequent interaction with cladding in LWRs was predicted by the rate theory modeling, providing valuable information for the development of U_{3}Si_{2} fuel as an accident-tolerant alternative for uranium dioxide.
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Neutrino Theory Neutrino Theory Understanding discoveries at the Energy, Intensity, and Cosmic Frontiers Get Expertise Rajan Gupta (505) 667-7664 Email Bruce Carlsten (505) 667-5657 Email Neutrino Theory solar neutrino Figure 1: Impact of the solar neutrino mass splitting on collective oscillations of supernova neutrinos. Notice that while the strictly vanishing splitting gives the two-flavor result, even a tiny nonzero value qualitatively changes the answer. From [1]. Neutrino physics underwent
Sanfilippo, Antonio P.
2005-12-27
Graph theory is a branch of discrete combinatorial mathematics that studies the properties of graphs. The theory was pioneered by the Swiss mathematician Leonhard Euler in the 18th century, commenced its formal development during the second half of the 19th century, and has witnessed substantial growth during the last seventy years, with applications in areas as diverse as engineering, computer science, physics, sociology, chemistry and biology. Graph theory has also had a strong impact in computational linguistics by providing the foundations for the theory of features structures that has emerged as one of the most widely used frameworks for the representation of grammar formalisms.
In-Situ TEM and DFT Study of Large Cation Transport and Failure Mechanism
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In Single SnO2 Nanowire - Joint Center for Energy Storage Research July 18, 2013, Research Highlights In-Situ TEM and DFT Study of Large Cation Transport and Failure Mechanism In Single SnO2 Nanowire (Top)Captured in-situ TEM movie frame showing the pristine SnO2 nanowire, displacement reaction upon Na insertion leads to two phases materials and the corresponding electron diffraction pattern. Upon desodiation, pore forms, leading to high impedence of the electrode. (Bottom) High resolution
Hong, Z.; Watwe, R.M.; Natal-Santiago, M.A.; Hill, J.M.; Dumesic, J.A.; Fogash, K.B.; Kim, B.; Masqueda-Jimenez, B.I.
1998-09-10
Reaction kinetics studies were conducted of isobutane and n-butane isomerization at 423 K over sulfated-zirconia, with the butane feeds purified of olefins. Dihydrogen evolution was observed during butane isomerization over fresh catalysts, as well as over catalysts selectively poisoned by preadsorbed ammonia. Butane isomerization over sulfated-zirconia can be viewed as a surface chain reaction comprised of initiation, propagation, and termination steps. The primary initiation step in the absence of feed olefins is considered to be the dehydrogenation of butane over sulfated-zirconia, generating butenes which adsorb onto acid sites to form protonated olefinic species associated with the conjugate base form of the acid sites. Quantum-chemical calculations, employing density-functional theory, suggest that the dissociative adsorption of dihydrogen, isobutylene hydrogenation, and dissociative adsorption of isobutane are feasible over the sulfated-zirconia cluster, and these reactions take place over Zr-O sites.
Kim, Inkoo; Lee, Yoon Sup
2014-10-28
We report the formulation and implementation of KRCASPT2, a two-component multi-configurational second-order perturbation theory based on Kramers restricted complete active space self-consistent field (KRCASSCF) reference function, in the framework of the spin-orbit relativistic effective core potential. The zeroth-order Hamiltonian is defined as the sum of nondiagonal one-electron operators with generalized two-component Fock matrix elements as scalar factors. The Kramers symmetry within the zeroth-order Hamiltonian is maintained via the use of a state-averaged density, allowing a consistent treatment of degenerate states. The explicit expressions are derived for the matrix elements of the zeroth-order Hamiltonian as well as for the perturbation vector. The use of a fully variational reference function and nondiagonal operators in relativistic multi-configurational perturbation theory is reported for the first time. A series of initial calculations are performed on the ionization potential and excitation energies of the atoms of the 6p-block; the results display a significant improvement over those from KRCASSCF, showing a closer agreement with experimental results. Accurate atomic properties of the superheavy elements of the 7p-block are also presented, and the electronic structures of the low-lying excited states are compared with those of their lighter homologues.
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PARATEC PARATEC Description PARATEC is a parallel, plane-wave basis, density functional theory (DFT) code developed at Berkeley. PARATEC is one of the DFT packages supported by the...
Electronic and spin transport properties of graphene nanoribbon...
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(QUAMBOs), a first-principles tight binding (TB) scheme based on density functional theory (DFT), combined with a non-equilibrium Green's function. For electronic transport,...
A comparative DFT study of the catalytic activity of the 3d transition metal sulphides surfaces
Gomez-Balderas, R.; Oviedo-Roa, R; Martinez-Magadan, J M.; Amador, C.; Dixon, David A. )
2002-10-10
The catalytic activity of the first transition metal series sulphides for hydrodesulfurization (HDS) reactions exhibits a particular behaviour when analysed as a function of the metal position in the Periodic Table. This work reports a comparative study of the electronic structure of the bulk and of the (0 0 1) metal surface (assumed to be the reactive surface) for the Sc-Zn monosulphides. The systems were modeled using the NiAs prototype crystal structure for the bulk and by applying the supercell model with seven atomic layers for (0 0 1) surfaces. The electronic structure of closed-packed solids code based on the density-functional theory and adopting the muffin-tin approximation to the potential was employed in the calculations of the electronic properties. For the Co and Ni sulphides, the density of states (DOS) variations between the metal atom present in the bulk and the ones exposed at the surface show that at the surface, there exists a higher DOS in the occupied states region just below the Fermi level. This feature might indicate a good performance of these two metal sulphides substrates in the HDS reactions favouring a donation, back-donation mechanism. In contrast, the DOS at the surface of Mn is increased in the unoccupied states region, just above the Fermi level. This suggests the possibility of a strong interaction with charge dontating sulphur adsorbate atoms poisoning the active substrate surface.
X-ray diffraction, spectroscopic and DFT studies of 1-(4-bromophenyl)-3,5-diphenylformazan
Tezcan, H.; Tokay, N.; Alpaslan, G.; Erdnmez, A.
2013-12-15
The crystal structure of 1-(4-bromophenyl)-3,5-diphenylformazan was determined by X-ray single crystal diffraction technique. The crystals are orthorhombic, a = 23.0788(9), b = 7.9606(3), c = 18.6340(12) , Z = 8, sp. gr. Pbca, R{sub 1} = 0.074. The structure was also examined using the density-functional theory. Its structure stability, and frontier molecular orbital components were discussed and the results were compared with X-ray and spectral results. The maximum absorbtion peaks of the UV-vis spectrum of the compound have been calculated using the time-dependent density-functional theory. It was found a good agreement between the calculated and experimental maximum absorption wavelength.
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Al-Hamdani, Yasmine S.; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos
2014-10-22
Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we showmore » that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B₃N₃H₆) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.« less
Al-Hamdani, Yasmine S.; Michaelides, Angelos; Alf, Dario; Lilienfeld, O. Anatole von
2014-11-14
Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B{sub 3}N{sub 3}H{sub 6}) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.
Pairing Nambu-Goldstone Modes within Nuclear Density Functional...
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Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory Citation Details ... Title: Pairing Nambu-Goldstone Modes within Nuclear Density Functional Theory Authors: ...
Interfacial Properties and Design of Functional Energy Materials
Sumpter, Bobby G [ORNL; Liang, Liangbo [ORNL; Nicolai, Adrien [Rensselaer Polytechnic Institute (RPI); Meunier, V. [Rensselaer Polytechnic Institute (RPI)
2014-01-01
The vital importance of energy to society continues to demand a relentless pursuit of energy responsive materials that can bridge fundamental chemical structures at the molecular level and achieve improved functionality, such as efficient energy conversion/storage/transmission, over multiple length scales. This demand can potentially be realized by harnessing the power of self-assembly a spontaneous process where molecules or much larger entities form ordered aggregates as a consequence of predominately non-covalent (weak) interactions. Self-assembly is the key to bottom-up design of molecular devices, because the nearly atomic-level control is very difficult to realize in a top-down, e.g., lithographic approach. However, while function (e.g., charge mobility) in simple systems such as single crystals can often be predicted, predicting the function of the great variety of self-assembled molecular architectures is complicated by the lack of understanding and control over nanoscale interactions, mesoscale architectures, and macroscale (long-range) order. To establish a foundation toward delivering practical solutions, it is critical to develop an understanding of the chemical and physical mechanisms responsible for the self-assembly of molecular and hybrid materials on various substrates. Typically molecular self-assembly involves poorly understood non-covalent intermolecular and substrate-molecule interactions compounded by local and/or collective influences from the substrate atomic lattice (symmetry and/or topological features) and electronic structure. Thus, progress towards unraveling the underlying physicochemical processes that control the structure and macroscopic physical, mechanical, electrical, and transport properties of materials increasingly requires tight integration of theory, modeling and simulation with precision synthesis, advanced experimental characterization, and device measurements. In this mode, theory and simulation can greatly accelerate the process of materials discovery by providing atomic level understanding of physicochemical phenomena and for making predictions of trends. In particular, this approach can provide understanding, prediction and exploration of new materials and conditions before they are realized in the lab, to illuminate connections between experimental observations, and help identify new materials for targeted synthesis. Toward this end, Density Functional Theory (DFT) can provide a suitable computational framework for investigating the inter- and intramolecular bonding, molecular conformation, charge and spin configurations that are intrinsic to self-assembly of molecules on substrates. This Account highlights recent advances in using an integrated approach based on DFT and scanning probe microscopy [STM(s), AFM] to study/develop electronic materials formed from the self-assembly of molecules into supramolecular or polymeric architectures on substrates. Here it is the interplay between molecular interactions and surface electrons that is used to control the final architecture and subsequent bulk properties of the two-dimensional patterns/assemblies. Indeed a rich variety of functional energy materials become possible.
DFT modeling of adsorption onto uranium metal using large-scale parallel computing
Davis, N.; Rizwan, U.
2013-07-01
There is a dearth of atomistic simulations involving the surface chemistry of 7-uranium which is of interest as the key fuel component of a breeder-burner stage in future fuel cycles. Recent availability of high-performance computing hardware and software has rendered extended quantum chemical surface simulations involving actinides feasible. With that motivation, data for bulk and surface 7-phase uranium metal are calculated in the plane-wave pseudopotential density functional theory method. Chemisorption of atomic hydrogen and oxygen on several un-relaxed low-index faces of 7-uranium is considered. The optimal adsorption sites (calculated cohesive energies) on the (100), (110), and (111) faces are found to be the one-coordinated top site (8.8 eV), four-coordinated center site (9.9 eV), and one-coordinated top 1 site (7.9 eV) respectively, for oxygen; and the four-coordinated center site (2.7 eV), four-coordinated center site (3.1 eV), and three-coordinated top2 site (3.2 eV) for hydrogen. (authors)
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Manifestation of Voltages on Pristine- and Thin SAND2015-2258C Film-Coated Lithium Battery (LIB) Electrodes Using electronic DFT-based calculations Kevin Leung Sandia National Laboratories 1. Devised methods for calibrating voltages 2. LIB surfaces can be charged 3. Need new conceptualization of "EDL" 4. Two "voltage" definitions: for e-, Li+ content 5. computational electrochemistry needs new capability, is not just applied Mater. Sci. Acknowledgement Andrew Leenheer, Craig
Structural, thermodynamic and optical properties of MgF{sub 2} studied from first-principles theory
Ramesh Babu, K.; Bheema Lingam, Ch.; Auluck, S.; Tewari, Surya P.; Vaitheeswaran, G.
2011-02-15
A detailed theoretical study of structural, electronic, elastic, thermodynamic and optical properties of rutile type MgF{sub 2} has been carried out by means of first-principles Density Functional Theory (DFT) calculations using plane wave pseudo-potentials within the local density approximation and generalized-gradient approximation for the exchange and correlation functionals. The calculated ground state properties and elastic constants agree quite well with experimental values. From the calculated elastic constants we conclude that MgF{sub 2} is relatively hard when compared to other alkaline-earth fluorides and ductile in nature. The thermodynamic properties such as heat capacity, entropy, free energy, phonon density of states and Debye temperatures are calculated at various temperatures from the lattice dynamical data obtained through the quasi-harmonic Debye model. From free energy and entropy it is found that the system is thermodynamically stable up to 1200 K. The imaginary part of the calculated dielectric function {epsilon}{sub 2}({omega}) could reproduce the six prominent peaks which are observed in experiment. From the calculated {epsilon}({omega}), other optical properties such as refractive index, reflectivity and electron energy-loss spectrum are obtained up to the photon energy range of 30 eV. -- Graphical abstract: The calculated imaginary part {epsilon}{sub 2}({omega}) of the complex dielectric function {epsilon}({omega}) of MgF{sub 2} as a function of photon energy is shown. The calculated {epsilon}{sub 2}({omega}) could reproduce the major peaks observed in experiment. All the peaks observed are corresponds to interband transitions from 'p' states of Fluorine in valence band to the 's' states of Mg in conduction band. Display Omitted Research highlights: > Structural and bonding properties. > Optical properties. > Single and polycrystalline elastic properties. > Thermodynamic properties.
Statistical Mechanics with Density Functional Theory Accuracy
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before the House Armed Services Subcommittee on Strategic Forces | National Nuclear Security Administration Statement on B61 Life Extension Program and Future Stockpile Strategy before the House Armed Services Subcommittee on Strategic Forces October 30, 2013 Introduction Chairman Rogers, Ranking Member Cooper and distinguished members of the Subcommittee, thank you for having me here to discuss the President's plans for nuclear weapon modernization focused on the B61 Life Extension Program
Li, Zhendong; Liu, Wenjian
2014-07-07
Analytic expressions for the first-order nonadiabatic coupling matrix elements between electronically excited states are first formulated exactly via both time-independent equation of motion and time-dependent response theory, and are then approximated at the configuration interaction singles, particle-hole/particle-particle random phase approximation, and time-dependent density functional theory/Hartree-Fock levels of theory. Note that, to get the Pulay terms arising from the derivatives of basis functions, the standard response theory designed for electronic perturbations has to be extended to nuclear derivatives. The results are further recast into a Lagrangian form that is similar to that for excited-state energy gradients and allows to use atomic orbital based direct algorithms for large molecules.
Karma Sawyer | Department of Energy
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at Berkeley in 2008, focusing on spin-crossover dynamics and homogeneous catalysis reactions using ultrafast infrared spectroscopy and density functional theory (DFT) calculations. ...
Tuning Pore Size to Enhance the Capacitance of Supercapacitors...
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ion diameter is a novel feature accurately predicted by molecular dynamics (MD) and qualitatively reproduced by the computationally more efficient density functional theory (DFT). ...
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effects. These challenges were overcome by applying state-of-the-art soft x-ray techniques in conjunction with hybrid density functional theory (DFT) calculations. To...
Center for Emergent Superconductivity (CES) | U.S. DOE Office...
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Center for Emergent Superconductivity (CES) Energy Frontier Research Centers (EFRCs) EFRCs ... neutron diffraction and scattering, density functional theory (DFT), monte carlo ...
Center for Understanding and Control of Acid Gas-induced Evolution...
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class of materials to accelerate materials discovery for large-scale energy applications. ... and scattering, molecular dynamics (MD), density functional theory (DFT), monte carlo ...
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... mantle are discussed. The state-of-the-art ultrasonic experiments performed in ... were investigated by Density Functional Theory (DFT) based first principles ...
Kyuho Lee | Center for Gas SeparationsRelevant to Clean Energy...
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frameworks (MOFs) and the electronic structures of them by means of first-principles dispersion-corrected density-functionals theory (DFT) calculations. The nonlocal van der Waals...
2009 Advanced Combustion Engine R&D Annual Report
Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site
... dark field scanning transmission electron microscopy ... We performed density functional theory (DFT) calculations in ... 2 O 3 substrate. Also in line with the experiments, our ...
Uncertainty Quantification and Propagation in Nuclear Density...
Office of Scientific and Technical Information (OSTI)
Nuclear density functional theory (DFT) is one of the main ... In particular, we cover the topics of parameter estimation for inverse problems, statistical analysis of model ...
Center for Defect Physics in Structural Materials - CDP
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LLNL Research Atomic and magnetic interactions treated using ab initio density functional theory (DFT). Quantum Monte Carlo (QMC) calculations of defect structures and energetics...
Walsh, Timothy Francis; Reese, Garth M.; Bhardwaj, Manoj Kumar
2011-11-01
Salinas provides a massively parallel implementation of structural dynamics finite element analysis, required for high fidelity, validated models used in modal, vibration, static and shock analysis of structural systems. This manual describes the theory behind many of the constructs in Salinas. For a more detailed description of how to use Salinas, we refer the reader to Salinas, User's Notes. Many of the constructs in Salinas are pulled directly from published material. Where possible, these materials are referenced herein. However, certain functions in Salinas are specific to our implementation. We try to be far more complete in those areas. The theory manual was developed from several sources including general notes, a programmer notes manual, the user's notes and of course the material in the open literature.
Theory of nodal s^{±}-wave pairing symmetry in the Pu-based 115 superconductor family
Das, Tanmoy; Zhu, Jian -Xin; Graf, Matthias J.
2015-02-27
The spin-fluctuation mechanism of superconductivity usually results in the presence of gapless or nodal quasiparticle states in the excitation spectrum. Nodal quasiparticle states are well established in copper-oxide, and heavy-fermion superconductors, but not in iron-based superconductors. Here, we study the pairing symmetry and mechanism of a new class of plutonium-based high-T_{c} superconductors and predict the presence of a nodal s⁺⁻ wave pairing symmetry in this family. Starting from a density-functional theory (DFT) based electronic structure calculation we predict several three-dimensional (3D) Fermi surfaces in this 115 superconductor family. We identify the dominant Fermi surface “hot-spots” in the inter-band scattering channel, which are aligned along the wavevector Q = (π, π, π), where degeneracy could induce sign-reversal of the pairing symmetry. Our calculation demonstrates that the s⁺⁻ wave pairing strength is stronger than the previously thought d-wave pairing; and more importantly, this pairing state allows for the existence of nodal quasiparticles. Finally, we predict the shape of the momentum- and energy-dependent magnetic resonance spectrum for the identification of this pairing symmetry.
Theory of nodal s±-wave pairing symmetry in the Pu-based 115 superconductor family
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Das, Tanmoy; Zhu, Jian -Xin; Graf, Matthias J.
2015-02-27
The spin-fluctuation mechanism of superconductivity usually results in the presence of gapless or nodal quasiparticle states in the excitation spectrum. Nodal quasiparticle states are well established in copper-oxide, and heavy-fermion superconductors, but not in iron-based superconductors. Here, we study the pairing symmetry and mechanism of a new class of plutonium-based high-Tc superconductors and predict the presence of a nodal s⁺⁻ wave pairing symmetry in this family. Starting from a density-functional theory (DFT) based electronic structure calculation we predict several three-dimensional (3D) Fermi surfaces in this 115 superconductor family. We identify the dominant Fermi surface “hot-spots” in the inter-band scattering channel,more » which are aligned along the wavevector Q = (π, π, π), where degeneracy could induce sign-reversal of the pairing symmetry. Our calculation demonstrates that the s⁺⁻ wave pairing strength is stronger than the previously thought d-wave pairing; and more importantly, this pairing state allows for the existence of nodal quasiparticles. Finally, we predict the shape of the momentum- and energy-dependent magnetic resonance spectrum for the identification of this pairing symmetry.« less
Li, Neng; Mo, Yuxiang; Ching, Wai-Yim
2013-11-14
In this work, we assess a full spectrum of properties (chemical bonding, charge distribution, spin ordering, optical, and elastic properties) of Cr{sub 2}AC (A = Al, Ge) and their hypothetical nitride counterparts Cr{sub 2}AN (A = Al, Ge) based on density functional theory calculations. The calculated total energy values indicate that a variety of spin ordering of these four compounds depending on interlayer-interactions between M-A and M-X within the sublattice, which is supported by bonding analysis. MAX phase materials are discovered to possess exotic magnetic properties which indicates that these materials could serve as promising candidates for novel layered magnetic materials for various electronic and spintronic applications. Further analysis of optical properties for two polarization vectors of Cr{sub 2}AX shows that the reflectivity is high in the visible-ultraviolet region up to ∼15 eV suggesting Cr{sub 2}AX as a promising candidate for use as a coating material. The elastic coefficients (C{sub ij}) and bulk mechanical properties [bulk modulus (K), shear modulus (G), Young's modulus (E), Poisson's ratio (η), and Pugh ratio (G/K)] of these four Cr{sub 2}AX compounds are also calculated and analyzed, which pave the way to predict or design new MAX phases that are less brittle or tougher by having a lower G/K value or higher η.
Neurock, Matthew
2011-05-26
The specific goal of this work was to understanding the catalytic reactions pathways for the synthesis of vinyl acetate over Pd, Au and PdAu alloys. A combination of both experimental methods (X-ray and Auger spectroscopies, low-energy ion scattering (LEIS), low-energy electron diffraction (LEED) and theory (Density Functional Theory (DFT) calculations and Monte Carlo methods under various different reactions) were used to track the surface chemistry and the influence of alloying. The surface intermediates involved in the various reactions were characterized using reflection-absorption infrared spectroscopy and LEED to identify the nature of the surface species and temperature-programmed desorption (TPD) to follow the decomposition pathways and measure heats of adsorption. These results along with those from density functional theoretical calculations were used determine the kinetics for elementary steps. The results from this work showed that the reaction proceeds via the Samanos mechanism over Pd surfaces whereby the ethylene directly couples with acetate to form an acetoxyethyl intermediate that subsequently undergoes a beta-hydride elimination to form the vinyl acetate monomer. The presence of Au was found to modify the adsorption energies and surface coverages of important surface intermediates including acetate, ethylidyne and ethylene which ultimately influences the critical C-H activation and coupling steps. By controlling the surface alloy composition or structure one can begin to control the steps that control the rate and even the mechanism.
Symplectic quantum mechanics and Chern-Simons gauge theory. I
Jeffrey, Lisa C.
2013-05-15
In this article we describe the relation between the Chern-Simons gauge theory partition function and the partition function defined using the symplectic action functional as the Lagrangian. We show that the partition functions obtained using these two Lagrangians agree, and we identify the semiclassical formula for the partition function defined using the symplectic action functional.
Asath, R. Mohamed; Premkumar, S.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin; Jawahar, A.
2015-06-24
The conformational analysis was carried out for 2-Hydroxy- 3, 5-dinitropyridine molecule using potential energy surface scan and the most stable optimized conformer was predicted. The vibrational frequencies and Mulliken atomic charge distribution were calculated for the optimized geometry of the molecule using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intramolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness values of the title molecule were carried out. The nonlinear optical activity of the molecule was studied by means of first order hyperpolarizability, which was computed as 7.64 times greater than urea. The natural bond orbital analysis was performed to confirm the nonlinear optical activity of the molecule.
Accurate nuclear masses from a three parameter Kohn-Sham DFT approach (BCPM)
Baldo, M.; Robledo, L. M.; Schuck, P.; Vinas, X.
2012-10-20
Given the promising features of the recently proposed Barcelona-Catania-Paris (BCP) functional [1], it is the purpose of this work to still improve on it. It is, for instance, shown that the number of open parameters can be reduced from 4-5 to 2-3, i.e. by practically a factor of two without deteriorating the results.
[Mathematics and string theory
Jaffe, A.; Yau, Shing-Tung.
1993-01-01
Work on this grant was centered on connections between non- commutative geometry and physics. Topics covered included: cyclic cohomology, non-commutative manifolds, index theory, reflection positivity, space quantization, quantum groups, number theory, etc.
Building a Universal Nuclear Energy Density Functional
Bertulani, Carlos A.
2014-09-10
This grant had two components: Density functional theory and pairing and Nuclear reactions. This final report summarizes the activities for this SciDAC-2 project.
Theory and Modeling Capabilities | Argonne National Laboratory
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Theory and Modeling Capabilities Theory and multiscale computer simulations provide the interpretive and predictive framework to understand fundamental processes and to aid in the design of functional nanoscale systems. Our primary facility is a high-performance computing cluster accommodating parallel computer-intensive applications. Capabilities Carbon High-Performance Computing Cluster (3000 cores, 30 GPUs, ~30 TeraFLOPS) Development tools (GNU and Intel compilers and math libraries) Density
Sierra Structural Dynamics Theory Manual
Reese, Garth M.
2015-10-19
Sierra/SD provides a massively parallel implementation of structural dynamics finite element analysis, required for high fidelity, validated models used in modal, vibration, static and shock analysis of structural systems. This manual describes the theory behind many of the constructs in Sierra/SD. For a more detailed description of how to use Sierra/SD , we refer the reader to Sierra/SD, User's Notes . Many of the constructs in Sierra/SD are pulled directly from published material. Where possible, these materials are referenced herein. However, certain functions in Sierra/SD are specific to our implementation. We try to be far more complete in those areas. The theory manual was developed from several sources including general notes, a programmer notes manual, the user's notes and of course the material in the open literature. This page intentionally left blank.
Makrlik, Emanuel; Toman, Petr; Vanura, Petr; Moyer, Bruce A
2013-01-01
From extraction experiments and c-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I (aq) + 1 (org),1Cs+ (org) + I (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logKex (1Cs+, I) = 2.1 0.1. Further, the stability constant of the 1Cs+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log borg (1Cs+) = 9.9 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complex species 1Cs+ was derived. In the resulting 1Cs+ complex, the central cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation p interaction.
Theory Modeling and Simulation
Shlachter, Jack
2012-08-23
Los Alamos has a long history in theory, modeling and simulation. We focus on multidisciplinary teams that tackle complex problems. Theory, modeling and simulation are tools to solve problems just like an NMR spectrometer, a gas chromatograph or an electron microscope. Problems should be used to define the theoretical tools needed and not the other way around. Best results occur when theory and experiments are working together in a team.
Lincoln, Don
2014-09-30
The Big Bang is the name of the most respected theory of the creation of the universe. Basically, the theory says that the universe was once smaller and denser and has been expending for eons. One common misconception is that the Big Bang theory says something about the instant that set the expansion into motion, however this isn’t true. In this video, Fermilab’s Dr. Don Lincoln tells about the Big Bang theory and sketches some speculative ideas about what caused the universe to come into existence.
Quantum Field Theory & Gravity
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begin? What is its large scale structure and evolution? How can gravity be unified with quantum mechanics and the Standard Model? Quantum Field Theory, Gravity & Cosmology There...
Krokhin, Arkadii
2014-04-18
New applications of the theory of homogenization for heterogeneous metamaterials, in particular for acoustic cloaking and for design and engineering of tunable phononic crystal.
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the phase-space integral ...III-1 I. S. Towner and J. C. Hardy The evaluation of V ud , experiment and theory ......
Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.
2015-08-30
Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with amore » chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.« less
Understanding oxygen adsorption on 9.375 at. % Ga-stabilized δ-Pu (111) surface: A DFT study
Hernandez, Sarah C.; Wilkerson, Marianne P.; Huda, Muhammad N.
2015-08-30
Plutonium (Pu) metal reacts rapidly in the presence of oxygen (O), resulting in an oxide layer that will eventually have an olive green rust appearance over time. Recent experimental work suggested that the incorporation of gallium (Ga) as an alloying impurity to stabilize the highly symmetric high temperature δ-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized δ-Pu (111) surface and investigated adsorption of atomic O using all-electron density functional theory. Key findings revealed that the O bonded strongly to a Pu-rich threefold hollow fcc site with a chemisorption energy of –5.06 eV. Migration of the O atom to a Pu-rich environment was also highly sensitive to the surface chemistry of the Pu–Ga surface; when the initial on-surface O adsorption site included a bond to a nearest neighboring Ga atom, the O atom relaxed to a Ga deficient environment, thus affirming the O preference for Pu. Only one calculated final on-surface O adsorption site included a Ga-O bond, but this chemisorption energy was energetically unfavorable. Chemisorption energies for interstitial adsorption sites that included a Pu or Pu-Ga environment suggested that over-coordination of the O atom was energetically unfavorable as well. Electronic structure properties of the on-surface sites, illustrated by the partial density of states, implied that the Ga 4p states indirectly but strongly influenced the Pu 6d states strongly to hybridize with the O 2p states, while also weakly influenced the Pu 5f states to hybridize with the O 2p states, even though Ga was not participating in bonding with O.
Theory, Simulation, and Computation
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ADTSC Theory, Simulation, and Computation Supporting the Laboratory's overarching strategy to provide cutting-edge tools to guide and interpret experiments and further our fundamental understanding and predictive capabilities for complex systems. Theory, modeling, informatics Suites of experiment data High performance computing, simulation, visualization Contacts Associate Director John Sarrao Deputy Associate Director Paul Dotson Directorate Office (505) 667-6645 Email Applying the Scientific
Theory, Modeling and Computation
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(Journal Article) | SciTech Connect Journal Article: Theory of Fano Resonances in Graphene: The Kondo effect probed by STM Citation Details In-Document Search Title: Theory of Fano Resonances in Graphene: The Kondo effect probed by STM We consider the theory of Kondo effect and Fano factor energy dependence for magnetic impurity (Co) on graphene. We have performed a first principles calculation and find that the two dimensional E{sub 1} representation made of d{sub xz}, d{sub yz} orbitals is
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Dark Matter Theory Dark Matter Theory Understanding discoveries at the Energy, Intensity, and Cosmic Frontiers Get Expertise Rajan Gupta (505) 667-7664 Email Bruce Carlsten (505) 667-5657 Email Dark Matter Theory The existence of dark matter can be traced back to the pioneering discoveries of Fritz Zwicky and Jan Oort that the motion of galaxies in the Coma cluster, and of nearby stars in our own Galaxy, do not follow the expected motion based on Newton's law of gravity and the observed visible
DOE R&D Accomplishments [OSTI]
Salam, A.
1956-04-01
Lectures with mathematical analysis are given on Dispersion Theory and Causality and Dispersion Relations for Pion-nucleon Scattering. The appendix includes the S-matrix in terms of Heisenberg Operators. (F. S.)
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Theory Center The Center for Theoretical and Computational Physics pursues a broad program of research in support of the physics being studied at Jefferson Lab and related facilities around the world. The Theory Center provides opportunities for interested scientists and students to visit the lab and work closely with theoretical and experimental colleagues.The center also advises the lab on the scientific merit of its program and its plans for future development. The center provides scientific
Nodal Diffusion & Transport Theory
Energy Science and Technology Software Center (OSTI)
1992-02-19
DIF3D solves multigroup diffusion theory eigenvalue, adjoint, fixed source, and criticality (concentration, buckling, and dimension search) problems in 1, 2, and 3-space dimensions for orthogonal (rectangular or cylindrical), triangular, and hexagonal geometries. Anisotropic diffusion theory coefficients are permitted. Flux and power density maps by mesh cell and regionwise balance integrals are provided. Although primarily designed for fast reactor problems, upscattering and internal black boundary conditions are also treated.
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the Fock matrix is constructed and then diagonalized. To build the Fock matrix, Fast Fourier Transforms are used to tranform orbitals from the plane wave basis ( where the...
Some Aspects of Reactor Theory
DOE R&D Accomplishments [OSTI]
Weinberg, Alvin M.
1952-10-10
Some general remarks are made on reactor theory, particularly the asymptotic theory and multigroup methods. Unsolved reactor problems are also briefly discussed. (B.J.H.)
Vector field theories in cosmology
Tartaglia, A.; Radicella, N.
2007-10-15
Recently proposed theories based on the cosmic presence of a vectorial field are compared and contrasted. In particular the so-called Einstein aether theory is discussed in parallel with a recent proposal of a strained space-time theory (cosmic defect theory). We show that the latter fits reasonably well the cosmic observed data with only one, or at most two, adjustable parameters, while other vector theories use much more. The Newtonian limits are also compared. Finally we show that the cosmic defect theory may be considered as a special case of the aether theories, corresponding to a more compact and consistent paradigm.
Theory of antiferromagnetic superconductors
Machida, K.; Nokura, K.; Matsubara, T.
1980-09-01
In this paper a theory is presented of antiferromagnetic superconductors in which a spin-density wave (SDW) ordering with a wave vector Q may coexist with superconductivity. The effect of the antiferromagnetic molecular field h/sub Q/(T) on the Cooper pairing is studied, and it is shown that, below the magnetic transition temperature T/sub N/' the Bardeen-Cooper-Schruffer coupling parameter is reduced by a factor of (1-constsuch thatub Q/(T)epsilon/sub F/) due to the formation of energy gaps of SDW on the Fermi surface along Q and this reduction can explain the anomaly in the upper critical field H/sub c/2 just below T/sub N/ as observed in RMo/sub 6/S/sub 8/ (R=Gd, Tb, and Dy). Taking account of both the spin-orbit scattering and spin-fluctuation effect near T/sub N/ in addition to the effect of h/sub Q/(T), a theoretical calculation of the superconducting transition temperature T/sub c/ and H/sub c/2(T) is performed. Detailed quantitative comparisons between theory and experiments on H/sub c/2(T) are made with fairly good accord for the above three compounds. Some speculation is given to discuss the remaining descrepancies between theory and experiments and certain phenomena not yet explained by the theory.
Barnes, Ted {F E }
2010-01-01
In this invited presentation, I review some recent developments in the theory of charmonium that appear likely to be of importance for future experimental studies in this field. The specific areas considered are double charmonium production. LQCD studies of charmonium, recent results for hadron loops, cc{bar} production cross sections at PANDA, charm molecules, and two recent developments, "charmiscelleny".
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III: NUCLEAR THEORY Astrophysical Factor for the Neutron Generator 13C(α16O Reaction in the AGB Stars ................................................................................III-1 A.M. Mukhamedzhanov, V.Z. Goldberg, G. Rogachev, E. Johnson, S. Brown, K. Kemper, A. Momotyuk, and B. Roeder The Trojan Horse Method: an Indirect Technique in Nuclear Astrophysics ......................................................................................................III-3 A.M. Mukhamedzhanov,
Benchmarking nuclear fission theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Bertsch, G. F.; Loveland, W.; Nazarewicz, W.; Talou, P.
2015-05-14
We suggest a small set of fission observables to be used as test cases for validation of theoretical calculations. Thus, the purpose is to provide common data to facilitate the comparison of different fission theories and models. The proposed observables are chosen from fission barriers, spontaneous fission lifetimes, fission yield characteristics, and fission isomer excitation energies.
Variational transition state theory
Truhlar, D.G.
1993-12-01
This research program involves the development of variational transition state theory (VTST) and semiclassical tunneling methods for the calculation of gas-phase reaction rates and selected applications. The applications are selected for their fundamental interest and/or their relevance to combustion.
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Theory & Modeling - Sandia Energy Energy Search Icon Sandia Home Locations Contact Us Employee Locator Energy & Climate Secure & Sustainable Energy Future Stationary Power Energy Conversion Efficiency Solar Energy Wind Energy Water Power Supercritical CO2 Geothermal Natural Gas Safety, Security & Resilience of the Energy Infrastructure Energy Storage Nuclear Power & Engineering Grid Modernization Battery Testing Nuclear Fuel Cycle Defense Waste Management Programs Advanced
Vortex operators in gauge field theories
Polchinski, J.
1980-07-01
Several related aspects of the 't Hooft vortex operator are studied. The current picture of the vacuum of quantum chromodynamics, the idea of dual field theories, and the idea of the vortex operator are reviewed first. The Abelian vortex operator written in terms of elementary fields and the calculation of its Green's functions are considered. A two-dimensional solvable model of a Dirac string is presented. The expression of the Green's functions more neatly in terms of Wu and Yang's geometrical idea of sections is addressed. The renormalization of the Green's functions of two kinds of Abelian looplike operators, the Wilson loop and the vortex operator, is studied; for both operators only an overall multiplicative renormalization is needed. In the case of the vortex this involves a surprising cancellation. Next, the dependence of the Green's functions of the Wilson and 't Hooft operators on the nature of the vacuum is discussed. The cluster properties of the Green's functions are emphasized. It is seen that the vortex operator in a massive Abelian theory always has surface-like clustering. The form of Green's functions in terms of Feynman graphs is the same in Higgs and symmetric phases; the difference appears in the sum over all tadpole trees. Finally, systems having fields in the fundamental representation are considered. When these fields enter only weakly into the dynamics, a vortex-like operator is anticipated. Any such operator can no longer be local looplike, but must have commutators at long range. A U(1) lattice gauge theory with two matter fields, one singly charged (fundamental) and one doubly charged (adjoint), is examined. When the fundamental field is weakly coupled, the expected phase transitions are found. When it is strongly coupled, the operator still appears to be a good order parameter, a discontinuous change in its behavior leads to a new phase transition. 18 figures.
Monoxides of small terbium clusters: A density functional theory investigation
Zhang, G. L.; Yuan, H. K. Chen, H.; Kuang, A. L.; Li, Y.; Wang, J. Z.; Chen, J.
2014-12-28
To investigate the effect of oxygen atom on the geometrical structures, electronic, and magnetic properties of small terbium clusters, we carried out the first-principles calculations on Tb{sub n}O (n = 1-14) clusters. The capping of an oxygen atom on one trigonal-facet of Tb{sub n} structures is always favored energetically, which can significantly improve the structural stability. The far-infrared vibrational spectroscopies are found to be different from those of corresponding bare clusters, providing a distinct signal to detect the characteristic structures of Tb{sub n}O clusters. The primary effect of oxygen atom on magnetic properties is to change the magnetic orderings among Tb atoms and to reduce small of local magnetic moments of the O-coordinated Tb atoms, both of which serve as the key reasons for the experimental magnetic evolution of an oscillating behavior. These calculations are consistent with, and help to account for, the experimentally observed magnetic properties of monoxide Tb{sub n}O clusters [C. N. Van Dijk et al., J. Appl. Phys. 107, 09B526 (2010)].
Quantum Electronic Stress: Density-Functional-Theory Formulation...
Office of Scientific and Technical Information (OSTI)
Additional Journal Information: Journal Volume: 109; Journal Issue: 5; Journal ID: ISSN 0031-9007 Publisher: American Physical Society Sponsoring Org: USDOE Country of...
Green's function multiple-scattering theory with a truncated...
Office of Scientific and Technical Information (OSTI)
American Physical Society Sponsoring Org: USDOE Country of Publication: United States Language: English Word Cloud More Like This Free Publicly Accessible Full Text Accepted...
Density Functional Theory Approach to Nuclear Fission (Conference...
Office of Scientific and Technical Information (OSTI)
DOE Contract Number: W-7405-ENG-48 Resource Type: Conference Resource Relation: Conference: Presented at: Zakopane Conference on Nuclear Physics, Zakopane, Poland, Aug 27 - Sep 02
The Materials Project: Combining Density Functional Theory Calculation...
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Facility Room 238 New materials can potentially reduce the cost and improve the efficiency of solar photovoltaics, batteries, and catalysts, leading to broad societal...
Density functional theory and conductivity studies of boron-based...
Office of Scientific and Technical Information (OSTI)
of primary carbon monofluoride (CFx) batteries, thereby preventing the clogging of ... are also potentially beneficial to rechargeable lithium ion and lithium air batteries. ...
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Functional Materials Researchers in NETL's Functional Materials Development competency work to discover and develop advanced functional materials and component processing technologies to meet technology performance requirements and enable scale-up for proof-of-concept studies. Research includes separations materials and electrochemical and magnetic materials, specifically: Separations Materials Synthesis, purification, and basic characterization of organic substances, including polymers and
Sandia National Laboratories: Page Title
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softening steel. April 2014 2013 Density Functional Theory (DFT) provides ab-initio, electronica structure based predictions of elastic-plastic constants in Ta, W, and Ta-W alloys....
GPAW | Argonne Leadership Computing Facility
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resource. Feedback Form GPAW What is GPAW? GPAW is a density-functional theory (DFT) Python code based on the projector-augmented wave (PAW) method. It uses real-space uniform...
Erickson, S.A. Jr.
1991-03-20
The purpose of this monograph is to start a theory of deterrence which has the capability of quantitatively answering the question of what is required to deter a nation or alliance from certain acts. Despite the existence of voluminous writing on deterrence, from the beginning of the nuclear age and even before, none of it attempts a theoretical discussion of how to calculate what it takes to deter a country from committing some acts which are objectionable to another country. Many theories of deterrence have already been created. They have exclusively been of two separate forms -- those of the social scientists, which deal with political questions, and how the concept of mass destruction psychological deters the initiation of war; and those of the mathematicians, who model the quantities of one country`s arsenal of strategic systems needed to destroy a certain portion of another country`s. Only the latter is quantitative, but they lack an essential element added to answer the question ``How much is enough?`` In order to use the techniques of operations research on the questions of what type and amount of weapons are adequate for deterrence, the definitions of quantities occurring in the calculations need to be made in quantifiable way. Numbers of weapons have been the only quantified parameter in previous deterrence calculations. Yet weapons alone do not deter. The threat of destruction and damage does. How is that threatenable damage to be measured, and as through defensive system construction, counterforce capability improvement, arms control, or other means, it becomes less when is the threshold for deterrence met and crossed? The calculation of this damage, and the implication of that damage to decision-makers capable of making a war initiation decision, is a complicated process, and it is what constitutes a theory of deterrence. 36 refs.
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Cascade B. Zhang, M. Gyulassy and C.M. Ko Charmonium Production from Hot Hadronic Matter C.M. Ko, X.N. Wang, B. Zhang and X.F. Zhang Excitation Function of Nucleon and Pion...
Cosmology in general massive gravity theories
Comelli, D.; Nesti, F.; Pilo, L. E-mail: fabrizio.nesti@aquila.infn.it
2014-05-01
We study the cosmological FRW flat solutions generated in general massive gravity theories. Such a model are obtained adding to the Einstein General Relativity action a peculiar non derivative potentials, function of the metric components, that induce the propagation of five gravitational degrees of freedom. This large class of theories includes both the case with a residual Lorentz invariance as well as the case with rotational invariance only. It turns out that the Lorentz-breaking case is selected as the only possibility. Moreover it turns out that that perturbations around strict Minkowski or dS space are strongly coupled. The upshot is that even though dark energy can be simply accounted by massive gravity modifications, its equation of state w{sub eff} has to deviate from -1. Indeed, there is an explicit relation between the strong coupling scale of perturbations and the deviation of w{sub eff} from -1. Taking into account current limits on w{sub eff} and submillimiter tests of the Newton's law as a limit on the possible strong coupling scale, we find that it is still possible to have a weakly coupled theory in a quasi dS background. Future experimental improvements on short distance tests of the Newton's law may be used to tighten the deviation of w{sub eff} form -1 in a weakly coupled massive gravity theory.
Raby, S.; Walker, T.; Babu, K.S.; Baer, H.; Balantekin, A.B.; Barger, V.; Berezhiani, Z.; de Gouvea, A.; Dermisek, R.; Dolgov, A.; Fileviez Perez, P.; Gabadadze, G.; Gal, A.; Gondolo, P.; Haxton, W.; Kamyshkov, Y.; Kayser, B.; Kearns, E.; Kopeliovich, B.; Lande, K.; Marfatia, D.; /Kansas U. /Maryland U. /Northeastern U. /UC, Berkeley /LBL, Berkeley /Minnesota U. /SLAC /UC, Santa Cruz /SUNY, Stony Brook /Oklahoma State U. /Iowa State U. /Carnegie Mellon U.
2011-11-14
The scientific case for a Deep Underground Science and Engineering Laboratory [DUSEL] located at the Homestake mine in Lead, South Dakota is exceptional. The site of this future laboratory already claims a discovery for the detection of solar neutrinos, leading to a Nobel Prize for Ray Davis. Moreover this work provided the first step to our present understanding of solar neutrino oscillations and a chink in the armor of the Standard Model of particle physics. We now know, from several experiments located in deep underground experimental laboratories around the world, that neutrinos have mass and even more importantly this mass appears to fit into the framework of theories which unify all the known forces of nature, i.e. the strong, weak, electromagnetic and gravitational. Similarly, DUSEL can forge forward in the discovery of new realms of nature, housing six fundamental experiments that will test the frontiers of our knowledge: (1) Searching for nucleon decay (the decay of protons and neutrons predicted by grand unified theories of nature); (2) Searching for neutrino oscillations and CP violation by detecting neutrinos produced at a neutrino source (possibly located at Brookhaven National Laboratory and/or Fermi National Laboratory); (3) Searching for astrophysical neutrinos originating from the sun, from cosmic rays hitting the upper atmosphere or from other astrophysical sources, such a supernovae; (4) Searching for dark matter particles (the type of matter which does not interact electromagnetically, yet provides 24% of the mass of the Universe); (5) Looking for the rare process known as neutrino-less double beta decay which is predicted by most theories of neutrino mass and allows two neutrons in a nucleus to spontaneously change into two protons and two electrons; and (6) Searching for the rare process of neutron- anti-neutron oscillations, which would establish violation of baryon number symmetry. A large megaton water Cherenkov detector for neutrinos and nucleon decay, located in DUSEL and roughly 20 times the size of current detectors, can perform the first three of these experiments. The last 3 can utilize the unique environment afforded by DUSEL to perform the most sensitive tests to date. Any one of these experiments can greatly increase our knowledge of nature. The Deep Underground Science and Engineering Laboratory (DUSEL), with a Large Megaton Size Detector, is desperately needed to address a set of fundamental issues in particle and astrophysics.
Chiral perturbation theory with nucleons
Meissner, U.G.
1991-09-01
I review the constraints posed on the interactions of pions, nucleons and photons by the spontaneously broken chiral symmetry of QCD. The framework to perform these calculations, chiral perturbation theory, is briefly discussed in the meson sector. The method is a simultaneous expansion of the Greens functions in powers of external moments and quark masses around the massless case, the chiral limit. To perform this expansion, use is made of a phenomenological Lagrangian which encodes the Ward-identities and pertinent symmetries of QCD. The concept of chiral power counting is introduced. The main part of the lectures of consists in describing how to include baryons (nucleons) and how the chiral structure is modified by the fact that the nucleon mass in the chiral limit does not vanish. Particular emphasis is put on working out applications to show the strengths and limitations of the methods. Some processes which are discussed are threshold photopion production, low-energy compton scattering off nucleons, {pi}N scattering and the {sigma}-term. The implications of the broken chiral symmetry on the nuclear forces are briefly described. An alternative approach, in which the baryons are treated as very heavy fields, is touched upon.
The Evolution of Soft Collinear Effective Theory
Lee, Christopher
2015-02-25
Soft Collinear Effective Theory (SCET) is an effective field theory of Quantum Chromodynamics (QCD) for processes where there are energetic, nearly lightlike degrees of freedom interacting with one another via soft radiation. SCET has found many applications in high-energy and nuclear physics, especially in recent years the physics of hadronic jets in e^{+}e^{-}, lepton-hadron, hadron-hadron, and heavy-ion collisions. SCET can be used to factorize multi-scale cross sections in these processes into single-scale hard, collinear, and soft functions, and to evolve these through the renormalization group to resum large logarithms of ratios of the scales that appear in the QCD perturbative expansion, as well as to study properties of nonperturbative effects. We overview the elementary concepts of SCET and describe how they can be applied in high-energy and nuclear physics.
{tau} decays and chiral perturbation theory
Colangelo, G.; Finkemeier, M.; Urech, R.
1996-10-01
In a small window of phase space, chiral perturbation theory can be used to make standard model predictions for {tau} decays into two and three pions. For {tau}{r_arrow}2{pi}{nu}{sub {tau}}, we give the analytical result for the relevant form factor {ital F}{sub {ital V}} up to two loops, then calculate the differential spectrum and compare with available data. For {tau}{r_arrow}3{pi}{nu}{sub {tau}}, we have calculated the hadronic matrix element to one loop. We discuss the decomposition of the three pion states into partition states and we give detailed predictions for the decay in terms of structure functions. We also compare with low energy predictions of meson dominance models. Overall, we find good agreement, but also some interesting discrepancies, which might have consequences beyond the limit of validity of chiral perturbation theory. {copyright} {ital 1996 The American Physical Society.}
The Evolution of Soft Collinear Effective Theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Lee, Christopher
2015-02-25
Soft Collinear Effective Theory (SCET) is an effective field theory of Quantum Chromodynamics (QCD) for processes where there are energetic, nearly lightlike degrees of freedom interacting with one another via soft radiation. SCET has found many applications in high-energy and nuclear physics, especially in recent years the physics of hadronic jets in e+e-, lepton-hadron, hadron-hadron, and heavy-ion collisions. SCET can be used to factorize multi-scale cross sections in these processes into single-scale hard, collinear, and soft functions, and to evolve these through the renormalization group to resum large logarithms of ratios of the scales that appear in the QCD perturbativemore » expansion, as well as to study properties of nonperturbative effects. We overview the elementary concepts of SCET and describe how they can be applied in high-energy and nuclear physics.« less
From Entropic Dynamics to Quantum Theory
Caticha, Ariel
2009-12-08
Non-relativistic quantum theory is derived from information codified into an appropriate statistical model. The basic assumption is that there is an irreducible uncertainty in the location of particles so that the configuration space is a statistical manifold. The dynamics then follows from a principle of inference, the method of Maximum Entropy. The concept of time is introduced as a convenient way to keep track of change. The resulting theory resembles both Nelson's stochastic mechanics and general relativity. The statistical manifold is a dynamical entity: its geometry determines the evolution of the probability distribution which, in its turn, reacts back and determines the evolution of the geometry. There is a new quantum version of the equivalence principle: 'osmotic' mass equals inertial mass. Mass and the phase of the wave function are explained as features of purely statistical origin.
ALS Evidence Confirms Combustion Theory
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ALS Evidence Confirms Combustion Theory Print Researchers recently uncovered the first step in the process that transforms gas-phase molecules into solid particles like soot and...
Shafi, Qaisar; Barr, Steven; Gaisser, Thomas; Stanev, Todor
2015-03-31
1. Executive Summary (April 1, 2012 - March 31, 2015) Title: Particle Theory, Particle Astrophysics and Cosmology Qaisar Shafi University of Delaware (Principal Investigator) Stephen M. Barr, University of Delaware (Co-Principal Investigator) Thomas K. Gaisser, University of Delaware (Co-Principal Investigator) Todor Stanev, University of Delaware (Co-Principal Investigator) The proposed research was carried out at the Bartol Research included Professors Qaisar Shafi Stephen Barr, Thomas K. Gaisser, and Todor Stanev, two postdoctoral fellows (Ilia Gogoladze and Liucheng Wang), and several graduate students. Five students of Qaisar Shafi completed their PhD during the period August 2011 - August 2014. Measures of the group’s high caliber performance during the 2012-2015 funding cycle included pub- lications in excellent refereed journals, contributions to working groups as well as white papers, and conference activities, which together provide an exceptional record of both individual performance as well as overall strength. Another important indicator of success is the outstanding quality of the past and current cohort of graduate students. The PhD students under our supervision regularly win the top departmental and university awards, and their publications records show excellence both in terms of quality and quantity. The topics covered under this grant cover the frontline research areas in today’s High Energy Theory & Phenomenology. For Professors Shafi and Barr they include LHC related topics including supersymmetry, collider physics, fl vor physics, dark matter physics, Higgs boson and seesaw physics, grand unifi and neutrino physics. The LHC two years ago discovered the Standard Model Higgs boson, thereby at least partially unlocking the secrets behind electroweak symmetry breaking. We remain optimistic that new and exciting physics will be found at LHC 14, which explain our focus on physics beyond the Standard Model. Professors Shafi continued his investigations in cosmology, specifically on supergravity and GUT infl models, primordial gravity waves, dark matter models. The origin of baryon and dark matter in the universe has been explored by Professors Barr and Shafi The research program of Professors Gaisser and Stanev address current research topics in Particle Astrophysics, in particular atmospheric and cosmogenic neutrinos and ultra-high energy cosmic rays. Work also included use of LHC data to improve tools for interpreting cascades generated in the atmosphere by high-energy particles from the cosmos. Cosmogenic neutrinos produced by interactions of ultra-high energy cosmic rays as they propagate through the cosmic microwave background radiation provides insight into the origin of the highest energy particles in nature. Overall, the research covered topics in the energy, cosmic and intensity frontiers.
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The nature of the low energy isovector dipole excitations in neutron rich nuclei................... III-1 E. Nica, D.C. Fuls, and S. Shlomo A modern nuclear energy density functional............................................................................ III-3 D. C. Fuls, V. K. Au, and S. Shlomo The Schiff moment and the isoscalar giant dipole resonance.................................................. III-5 N. Auerbach and S. Shlomo An improved calculation of the isospin-symmetry-breaking
Energy Science and Technology Software Center (OSTI)
1986-05-01
The ALTERNATIVE LIBRARY is a library of elementary functions prepared for use with the standard FORTRAN compiler under 4.2 BSD UNIX as an alternative to the standard system library. The library offers improved accuracy as well as additional capabilities. It includes routines ASIN, ACOS, COSH, EXP, LOG, LOG10, POW, SIN, COS, SINH, TAN, and TANH. These alternative routines have slightly modified domains and slightly different responses to invalid arguments. Four routines, not part of themore » standard library, are provided: ADX(X,N), a double-precision function that returns the double-precision argument X scaled by 2 raised to the Nth power; INTXP(X), an integer function that returns as a signed integer the exponent of the double-precision argument X; SETXP(X,N), a double-precision function that returns the double-precision argument X with its exponent replaced by N; and DCOTAN(X), a double-precision function that returns the cotangent of the double-precision argument X, where X is given in radians.« less
Neoclassical Theory and Its Applications
Shaing, Ker-Chung
2015-11-20
The grant entitled Neoclassical Theory and Its Applications started on January 15 2001 and ended on April 14 2015. The main goal of the project is to develop neoclassical theory to understand tokamak physics, and employ it to model current experimental observations and future thermonuclear fusion reactors. The PI had published more than 50 papers in refereed journals during the funding period.
Geometric scalar theory of gravity
Novello, M.; Bittencourt, E.; Goulart, E.; Salim, J.M.; Toniato, J.D.; Moschella, U. E-mail: eduhsb@cbpf.br E-mail: egoulart@cbpf.br E-mail: toniato@cbpf.br
2013-06-01
We present a geometric scalar theory of gravity. Our proposal will be described using the ''background field method'' introduced by Gupta, Feynman, Deser and others as a field theory formulation of general relativity. We analyze previous criticisms against scalar gravity and show how the present proposal avoids these difficulties. This concerns not only the theoretical complaints but also those related to observations. In particular, we show that the widespread belief of the conjecture that the source of scalar gravity must be the trace of the energy-momentum tensor which is one of the main difficulties to couple gravity with electromagnetic phenomenon in previous models does not apply to our geometric scalar theory. From the very beginning this is not a special relativistic scalar gravity. The adjective ''geometric'' pinpoints its similarity with general relativity: this is a metric theory of gravity. Some consequences of this new scalar theory are explored.
Chiral anomalies and zeta-function regularization
Reuter, M.
1985-03-15
The zeta-function method for regularizing determinants is used to calculate the chiral anomalies of several field-theory models. In SU(N) gauge theories without ..gamma../sub 5/ couplings, the results of perturbation theory are obtained in an unambiguous manner for the full gauge theory as well as for the corresponding external-field problem. If axial-vector couplings are present, different anomalies occur for the two cases. The result for the full gauge theory is again uniquely determined; for its nongauge analog, however, ambiguities can arise. The connection between the basic path integral and the operator used to construct the heat kernel is investigated and the significance of its Hermiticity and gauge covariance are analyzed. The implications of the Wess-Zumino conditions are considered.
Das, Ujjal; Zhang, Guanghui; Hu, Bo; Hock, Adam S.; Redfern, Paul C.; Miller, Jeffrey T.; Curtiss, Larry A.
2015-12-01
Amorphous silica (SiO2) is commonly used as a support in heterogeneous catalysis. However, due to the structural disorder and temperature induced change of surface morphology, the structures of silica supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory calculations to understand the effect of siloxane ring strain on structure and activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal-silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and, a correlation between metal-silanol interaction energy and ring strain energy has been observed. In addition to ring strain, the strength of the metal-silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal-silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the EXAFS data of monomeric Zn(II) and Ga(III) ions grafted on silica. The molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.
Quantum Field Theory & Gravity
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Quantum Field Theory & Gravity Quantum Field Theory & Gravity Understanding discoveries at the Energy, Intensity, and Cosmic Frontiers Get Expertise Rajan Gupta (505) 667-7664 Email Bruce Carlsten (505) 667-5657 Email Quantum Field Theory and Gravity at Los Alamos The HEP effort at Los Alamos in this area is actively pursing a number of questions in this area. What is the final state of complete gravitational collapse? What happens at the event horizon? What is dark energy? How did the
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
mFUSE: Function Sequencer for MATLAB Help Manual LANL/UCSD Engineering Institute LA-CC-10-033 LA-UR 10-01264 c Copyright 2010, Los Alamos National Security, LLC All rights reserved. July 29, 2010 LA-CC-10-033 LA-UR 10-01264 Contents I What is mFUSE? 4 1 Features . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2 Version Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . 6 3 About This Manual . . . . . . . . . . . . . . . . . . . . . . . . 6 4 Author Information . . . . .
Mardirossian, Narbe; Head-Gordon, Martin
2014-05-14
The limit of accuracy for semi-empirical generalized gradient approximation (GGA) density functionals is explored by parameterizing a variety of local, global hybrid, and range-separated hybrid functionals. The training methodology employed differs from conventional approaches in 2 main ways: (1) Instead of uniformly truncating the exchange, same-spin correlation, and opposite-spin correlation functional inhomogeneity correction factors, all possible fits up to fourth order are considered, and (2) Instead of selecting the optimal functionals based solely on their training set performance, the fits are validated on an independent test set and ranked based on their overall performance on the training and test sets. The 3 different methods of accounting for exchange are trained both with and without dispersion corrections (DFT-D2 and VV10), resulting in a total of 491508 candidate functionals. For each of the 9 functional classes considered, the results illustrate the trade-off between improved training set performance and diminished transferability. Since all 491508 functionals are uniformly trained and tested, this methodology allows the relative strengths of each type of functional to be consistently compared and contrasted. The range-separated hybrid GGA functional paired with the VV10 nonlocal correlation functional emerges as the most accurate form for the present training and test sets, which span thermochemical energy differences, reaction barriers, and intermolecular interactions involving lighter main group elements.
ALS Evidence Confirms Combustion Theory
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
ALS Evidence Confirms Combustion Theory ALS Evidence Confirms Combustion Theory Print Wednesday, 22 October 2014 11:43 Researchers recently uncovered the first step in the process that transforms gas-phase molecules into solid particles like soot and other carbon-based compounds. It's a discovery that could help combustion chemists make more efficient, less polluting fuels and help materials scientists fine-tune their carbon nanotubes and graphene sheets for faster, smaller electronics. In
Cabao, M. Isabel, E-mail: isabelcabaco@ist.utl.pt [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica Atmica da UL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Besnard, Marcel; Danten, Yann [GSM Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Chvez, Fabin Vaca [Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Pinaud, Nol [CESAMO Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Sebastio, Pedro J. [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Coutinho, Joo A. P. [CICECO, Departamento de Qumica, Universidade de Aveiro 3810-193 Aveiro (Portugal)
2014-06-28
NMR spectroscopy ({sup 1}H, {sup 13}C, {sup 15}N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS{sub 2} leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH{sub 3}COS{sup ?}), CO{sub 2}, OCS, and trithiocarbonate (CS{sub 3}{sup 2?}). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro]{sup +} cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS{sub 2}-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO{sub 2}-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS{sub 2} reacts with the acetate anion leading to the formation of CH{sub 3}COS{sup ?}, CO{sub 2}, and OCS. After these reactions have proceeded the nascent CO{sub 2} and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO{sub 2}) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO{sub 2}-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO{sub 2} molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO{sub 2}, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS{sub 2} is unfavoured and that the anion offers a competitive reactive channel via an oxygen-sulphur exchange mechanism with the solute in systems (1) and (2)
The General Theory of Relativity - F
Office of Scientific and Technical Information (OSTI)
... The Evolution of Physics by Albert Einstein and Leopold Infeld Traces the main ideas of physics from Galileo to modern quantum theory in four chapters. Relativity theory, including ...
Thermoelectric Materials by Design, Computational Theory and...
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by Design, Computational Theory and Structure Thermoelectric Materials by Design, Computational Theory and Structure 2009 DOE Hydrogen Program and Vehicle Technologies Program...
The General Theory of Relativity - A
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Einstein's special theory of relativity addressed the problem of the invariant speed of light in vacuum by showing the interrelationship of space and time. The general theory of ...
Analytical theory of coherent synchrotron radiation wakefield...
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Analytical theory of coherent synchrotron radiation wakefield of short bunches shielded by conducting parallel plates Citation Details In-Document Search Title: Analytical theory ...
Optical Abelian lattice gauge theories
Tagliacozzo, L.; Celi, A.; Zamora, A.; Lewenstein, M.; ICREA-Institucio Catalana de Recerca i Estudis Avancats, 08010 Barcelona
2013-03-15
We discuss a general framework for the realization of a family of Abelian lattice gauge theories, i.e., link models or gauge magnets, in optical lattices. We analyze the properties of these models that make them suitable for quantum simulations. Within this class, we study in detail the phases of a U(1)-invariant lattice gauge theory in 2+1 dimensions, originally proposed by P. Orland. By using exact diagonalization, we extract the low-energy states for small lattices, up to 4 Multiplication-Sign 4. We confirm that the model has two phases, with the confined entangled one characterized by strings wrapping around the whole lattice. We explain how to study larger lattices by using either tensor network techniques or digital quantum simulations with Rydberg atoms loaded in optical lattices, where we discuss in detail a protocol for the preparation of the ground-state. We propose two key experimental tests that can be used as smoking gun of the proper implementation of a gauge theory in optical lattices. These tests consist in verifying the absence of spontaneous (gauge) symmetry breaking of the ground-state and the presence of charge confinement. We also comment on the relation between standard compact U(1) lattice gauge theory and the model considered in this paper. - Highlights: Black-Right-Pointing-Pointer We study the quantum simulation of dynamical gauge theories in optical lattices. Black-Right-Pointing-Pointer We focus on digital simulation of abelian lattice gauge theory. Black-Right-Pointing-Pointer We rediscover and discuss the puzzling phase diagram of gauge magnets. Black-Right-Pointing-Pointer We detail the protocol for time evolution and ground-state preparation in any phase. Black-Right-Pointing-Pointer We provide two experimental tests to validate gauge theory quantum simulators.
Active Oxygen Vacancy Site for Methanol Synthesis from CO2 Hydrogenation on In2O3(110): A DFT Study
Ye, Jingyun; Liu, Changjun; Mei, Donghai; Ge, Qingfeng
2013-06-03
Methanol synthesis from CO2 hydrogenation on the defective In2O3(110) surface with surface oxygen vacancies has been investigated using periodic density functional theory calculations. The relative stabilities of six possible surface oxygen vacancies numbered from Ov1 to Ov6 on the perfect In2O3(110) surface were examined. The calculated oxygen vacancy formation energies show that the D1 surface with the Ov1 defective site is the most thermodynamically favorable while the D4 surface with the Ov4 defective site is the least stable. Two different methanol synthesis routes from CO2 hydrogenation over both D1 and D4 surfaces were studied and the D4 surface was found to be more favorable for CO2 activation and hydrogenation. On the D4 surface, one of the O atoms of the CO2 molecule fills in the Ov4 site upon adsorption. Hydrogenation of CO2 to HCOO on the D4 surface is both thermodynamically and kinetically favorable. Further hydrogenation of HCOO involves both forming the C-H bond and breaking the C-O bond, resulting in H2CO and hydroxyl. The HCOO hydrogenation is slightly endothermic with an activation barrier of 0.57 eV. A high barrier of 1.14 eV for the hydrogenation of H2CO to H3CO indicates that this step is the rate-limiting step in the methanol synthesis on the defective In2O3(110) surface. We gratefully acknowledge the supports from the National Natural Science Foundation of China (#20990223) and from US Department of Energy, Basic Energy Science program (DE-FG02-05ER46231). D. Mei was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory in Richland, Washington. PNNL is a multiprogram national laboratory operated for DOE by Battelle.
Dark matter signals at neutrino telescopes in effective theories
Catena, Riccardo
2015-04-29
We constrain the effective theory of one-body dark matter-nucleon interactions using neutrino telescope observations. We derive exclusion limits on the 28 coupling constants of the theory, exploring interaction operators previously considered in dark matter direct detection only, and using new nuclear response functions recently derived through nuclear structure calculations. We determine for what interactions neutrino telescopes are superior to current direct detection experiments, and show that Hydrogen is not the most important element in the exclusion limit calculation for the majority of the spin-dependent operators.
Resilience: Theory and Application.
Carlson, J.L.; Haffenden, R.A.; Bassett, G.W.; Buehring, W.A.; Collins, M.J., III; Folga, S.M.; Petit, F.D.; Phillips, J.A.; Verner, D.R.; Whitfield, R.G.
2012-02-03
There is strong agreement among policymakers, practitioners, and academic researchers that the concept of resilience must play a major role in assessing the extent to which various entities - critical infrastructure owners and operators, communities, regions, and the Nation - are prepared to respond to and recover from the full range of threats they face. Despite this agreement, consensus regarding important issues, such as how resilience should be defined, assessed, and measured, is lacking. The analysis presented here is part of a broader research effort to develop and implement assessments of resilience at the asset/facility and community/regional levels. The literature contains various definitions of resilience. Some studies have defined resilience as the ability of an entity to recover, or 'bounce back,' from the adverse effects of a natural or manmade threat. Such a definition assumes that actions taken prior to the occurrence of an adverse event - actions typically associated with resistance and anticipation - are not properly included as determinants of resilience. Other analyses, in contrast, include one or more of these actions in their definitions. To accommodate these different definitions, we recognize a subset of resistance- and anticipation-related actions that are taken based on the assumption that an adverse event is going to occur. Such actions are in the domain of resilience because they reduce both the immediate and longer-term adverse consequences that result from an adverse event. Recognizing resistance- and anticipation-related actions that take the adverse event as a given accommodates the set of resilience-related actions in a clear-cut manner. With these considerations in mind, resilience can be defined as: 'the ability of an entity - e.g., asset, organization, community, region - to anticipate, resist, absorb, respond to, adapt to, and recover from a disturbance.' Because critical infrastructure resilience is important both in its own right and because of its implications for community/regional resilience, it is especially important to develop a sound methodology for assessing resilience at the asset/facility level. This objective will be accomplished by collecting data on four broadly defined groups of resilience-enhancing measures: preparedness, mitigation measures, response capabilities, and recovery mechanisms. Table ES-1 illustrates how the six components that define resilience are connected to the actions that enhance the capacity of an entity to be resilient. The relationships illustrated in Table ES-1 provide the framework for developing a survey instrument that will be used to elicit the information required to assess resilience at the asset/facility level. The resilience of a community/region is a function of the resilience of its subsystems, including its critical infrastructures, economy, civil society, governance (including emergency services), and supply chains/dependencies. The number and complexity of these subsystems will make the measurement of resilience more challenging as we move from individual assets/facilities to the community/regional level (where critical infrastructure resilience is only one component). Specific challenges include uncertainty about relationships (e.g., the composition of specific supply chains), data gaps, and time and budget constraints that prevent collection of all of the information needed to construct a comprehensive assessment of the resilience of a specific community or region. These challenges can be addressed, at least partially, by adopting a 'systems approach' to the assessment of resilience. In a systems approach, the extent to which the analysis addresses the resilience of the individual subsystems can vary. Specifically, high-level systems analysis can be used to identify the most important lower-level systems. In turn, within the most important lower-level systems, site assessment data should be collected only on the most critical asset-level components about which the least is known. Implementation of the strategies outlined here to assess resilience will facilitate the following four objectives: (1) Develop a methodology and supporting products to assess resilience at the asset/facility level, (2) Develop a methodology and supporting products to assess resilience at the critical infrastructure sector level, (3) Provide resilience-related information to critical infrastructure owners/operators to facilitate risk-based resource decision making, and (4) Provide resilience-related information to State and local mission partners to support their risk-based resource decision making.
Sderlind, P. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Landa, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Turchi, P. E. A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
2014-10-01
In a recent paper, Xie et al. [Phys. Rev. B 88, 235128 (2013)], report that the density-functional theory (DFT) with the so-called DFT plus Hubbard U (DFT+U) modification improves energetics, volumes, and formation enthalpies over the standard form of DFT for uranium metal and U-Zr alloys. Also, spin-orbit coupling (SOC) was argued to advance the aforementioned properties in these systems. We demonstrate, contrarily, that neither the Hubbard U approach nor SOC is necessary for a correct description of uranium metal and U-Zr alloys. We further illustrate that the combination of DFT+U and SOC in the projector augmented-wave calculations by Xie et al. results in unrealistically large volume expansions, particularly for ?-U, in stark contrast to all previous calculations for elemental uranium. This in turn may also explain why the DFT+U with SOC model predicts negative enthalpy of mixing in the U-Zr alloy system contradicting conventional DFT as well as one of the main features of the experimental U-Zr phase diagram. The assertion by Xie et al. that DFT+U is an improvement over DFT for these systems is illustrated to be incorrect.
Double field theory inspired cosmology
Wu, Houwen; Yang, Haitang E-mail: hyanga@scu.edu.cn
2014-07-01
Double field theory proposes a generalized spacetime action possessing manifest T-duality on the level of component fields. We calculate the cosmological solutions of double field theory with vanishing Kalb-Ramond field. It turns out that double field theory provides a more consistent way to construct cosmological solutions than the standard string cosmology. We construct solutions for vanishing and non-vanishing symmetry preserving dilaton potentials. The solutions assemble the pre- and post-big bang evolutions in one single line element. Our results show a smooth evolution from an anisotropic early stage to an isotropic phase without any special initial conditions in contrast to previous models. In addition, we demonstrate that the contraction of the dual space automatically leads to both an inflation phase and a decelerated expansion of the ordinary space during different evolution stages.
Plasma Confinement Theory and Modeling
David W. Ross
2003-03-31
OAK-B188 The FRC Theory Program has for years been devoted to understanding tokamak confinement through the comparison of experimental data with theory and theoretical models. This work supported the FRC Experimental Program on TEXT and TEXT-U, especially in the interpretation of fluctuation data and its relation to transport. In recent years, the experimentalists have been conducting turbulence measurements on DIII-D and are preparing to do so on ALCATOR C-MOD. The Theory Group collaborated in these studies by means of turbulence simulation. We also broadened our effort to participate in the National Transport Code Collaboration (NTCC) and the National Compact Stellarator Program. Our purpose has been both to participate more fully in the fusion program generally and to collaborate with FRC experimental programs on existing or new machines.
Complex-energy approach to sum rules within nuclear density functional...
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Complex-energy approach to sum rules within nuclear density functional theory Citation ... This content will become publicly available on April 27, 2016 Title: Complex-energy ...
Complex-energy approach to sum rules within nuclear density functional...
Office of Scientific and Technical Information (OSTI)
Journal Article: Complex-energy approach to sum rules within nuclear density functional theory Citation Details In-Document Search This content will become publicly available on...
Geometry, topology, and string theory
Varadarajan, Uday
2003-07-10
A variety of scenarios are considered which shed light upon the uses and limitations of classical geometric and topological notions in string theory. The primary focus is on situations in which D-brane or string probes of a given classical space-time see the geometry quite differently than one might naively expect. In particular, situations in which extra dimensions, non-commutative geometries as well as other non-local structures emerge are explored in detail. Further, a preliminary exploration of such issues in Lorentzian space-times with non-trivial causal structures within string theory is initiated.
Shortcuts to adiabaticity from linear response theory
Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian
2015-10-23
A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. Moreover, with the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. We finally propose a degenerate family of protocols, which facilitates shortcuts to adiabaticity for specific and very short driving times.
Shortcuts to adiabaticity from linear response theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Acconcia, Thiago V.; Bonança, Marcus V. S.; Deffner, Sebastian
2015-10-23
A shortcut to adiabaticity is a finite-time process that produces the same final state as would result from infinitely slow driving. We show that such shortcuts can be found for weak perturbations from linear response theory. Moreover, with the help of phenomenological response functions, a simple expression for the excess work is found—quantifying the nonequilibrium excitations. For two specific examples, i.e., the quantum parametric oscillator and the spin 1/2 in a time-dependent magnetic field, we show that finite-time zeros of the excess work indicate the existence of shortcuts. We finally propose a degenerate family of protocols, which facilitates shortcuts tomore » adiabaticity for specific and very short driving times.« less
Effective field theory for a heavy Higgs boson: A manifestly gauge-invariant approach
Nyffeler, A.; Schenk, A.
1996-02-01
For large values of the Higgs boson mass the low energy structure of the gauged linear {sigma} model in the spontaneously broken phase can adequately be described by an effective field theory. In this work we present a manifestly gauge-invariant technique to explicitly evaluate the corresponding effective Langrangian from the underlying theory. In order to demonstrate the application of this functional method, the effective field theory of the Abelian Higgs model is thoroughly analyzed. We stress that this technique does not rely on any particular property of the Abelian case. The application to the non-Abelian theory is outlined. {copyright} {ital 1996 The American Physical Society.}
Plasma theory and simulation research
Birdsall, C.K.
1989-01-01
Our research group uses both theory and simulation as tools in order to increase the understanding of instabilities, heating, diffusion, transport and other phenomena in plasmas. We also work on the improvement of simulation, both theoretically and practically. Our focus has been more and more on the plasma edge (the sheath''), interactions with boundaries, leading to simulations of whole devices (someday a numerical tokamak).
Interpolating the Coulomb phase of little string theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Lin, Ying -Hsuan; Shao, Shu -Heng; Wang, Yifan; Yin, Xi
2015-12-03
We study up to 8-derivative terms in the Coulomb branch effective action of (1,1) little string theory, by collecting results of 4-gluon scattering amplitudes from both perturbative 6D super-Yang-Mills theory up to 4-loop order, and tree-level double scaled little string theory (DSLST). In previous work we have matched the 6-derivative term from the 6D gauge theory to DSLST, indicating that this term is protected on the entire Coulomb branch. The 8-derivative term, on the other hand, is unprotected. In this paper we compute the 8-derivative term by interpolating from the two limits, near the origin and near the infinity onmore » the Coulomb branch, numerically from SU(k) SYM and DSLST respectively, for k=2,3,4,5. We discuss the implication of this result on the UV completion of 6D SYM as well as the strong coupling completion of DSLST. As a result, we also comment on analogous interpolating functions in the Coulomb phase of circle-compactified (2,0) little string theory.« less
Lattice cluster theory for dense, thin polymer films
Freed, Karl F.
2015-04-07
While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L − 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential “transport” constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends.
Twisted noncommutative field theory with the Wick-Voros and Moyal products
Galluccio, Salvatore; Lizzi, Fedele; Vitale, Patrizia
2008-10-15
We present a comparison of the noncommutative field theories built using two different star products: Moyal and Wick-Voros (or normally ordered). For the latter we discuss both the classical and the quantum field theory in the quartic potential case and calculate the Green's functions up to one loop, for the two- and four-point cases. We compare the two theories in the context of the noncommutative geometry determined by a Drinfeld twist, and the comparison is made at the level of Green's functions and S matrix. We find that while the Green's functions are different for the two theories, the S matrix is the same in both cases and is different from the commutative case.
Variational perturbation theory and nonperturbative calculations in QCD
Solovtsova, O. P.
2013-10-15
A nonperturbative approach based on the variational perturbation theory in quantum chromodynamics is developed. The variational series is different from the conventional perturbative expansion and can be used to go beyond the weak-coupling regime. The approach suggested takes into account the summation of threshold singularities and the involvement of nonperturbative light quark masses. Phenomenological applications of this approach to describe physical quantities connected with the hadronic {tau}-decay data: the R{sub {tau}} ratio, the light-quark Adler function, and the smeared R{sub {Delta}} function are presented. The description of examined quantities includes an infrared region and, therefore, they cannot be directly calculated within the standard perturbation theory. It is shown that in spite of this fact the approach suggested gives a rather good result for these quantities down to the lowest energy scale.
2009 Section III: Nuclear Theory
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interaction of nucleons with mini black holes A. M. Mukhamedzhanov and L. Greenspan Atomic overlap correction to the statistical rate function I. S. Towner and J. C....
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Science Drivers: Theory Stefan H¨ oche SLAC National Accelerator Laboratory DOE Exascale Requirements Review (HEP) June 10, 2015 P5 recommendations [http://www.usparticlephysics.org/p5] From the summary: Specific investments in particle accelerator, instrumentation, and computing research and development are required to support the program and to ensure the long-term productivity of the field. From the report: Computing cuts across all activities in particle physics, and these activities spur
Beyond the Standard Model Theory
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Beyond the Standard Model Theory Beyond the Standard Model Understanding discoveries at the Energy, Intensity, and Cosmic Frontiers Get Expertise Rajan Gupta (505) 667-7664 Email Bruce Carlsten (505) 667-5657 Email LHC physics at Los Alamos The Large Hadron Collider (LHC) is studying the structure of matter at sub-nucleon distance scales by colliding protons together at high center of mass energy. The LHC has a broad scientific program, performing studies of QCD, heavy quarks, the W and Z
ALS Evidence Confirms Combustion Theory
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ALS Evidence Confirms Combustion Theory Print Researchers recently uncovered the first step in the process that transforms gas-phase molecules into solid particles like soot and other carbon-based compounds. It's a discovery that could help combustion chemists make more efficient, less polluting fuels and help materials scientists fine-tune their carbon nanotubes and graphene sheets for faster, smaller electronics. In addition, the results could have implications for the burgeoning field of
ALS Evidence Confirms Combustion Theory
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
ALS Evidence Confirms Combustion Theory Print Researchers recently uncovered the first step in the process that transforms gas-phase molecules into solid particles like soot and other carbon-based compounds. It's a discovery that could help combustion chemists make more efficient, less polluting fuels and help materials scientists fine-tune their carbon nanotubes and graphene sheets for faster, smaller electronics. In addition, the results could have implications for the burgeoning field of
ALS Evidence Confirms Combustion Theory
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
ALS Evidence Confirms Combustion Theory Print Researchers recently uncovered the first step in the process that transforms gas-phase molecules into solid particles like soot and other carbon-based compounds. It's a discovery that could help combustion chemists make more efficient, less polluting fuels and help materials scientists fine-tune their carbon nanotubes and graphene sheets for faster, smaller electronics. In addition, the results could have implications for the burgeoning field of
ALS Evidence Confirms Combustion Theory
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
ALS Evidence Confirms Combustion Theory Print Researchers recently uncovered the first step in the process that transforms gas-phase molecules into solid particles like soot and other carbon-based compounds. It's a discovery that could help combustion chemists make more efficient, less polluting fuels and help materials scientists fine-tune their carbon nanotubes and graphene sheets for faster, smaller electronics. In addition, the results could have implications for the burgeoning field of
Fermilab | Science at Fermilab | Theory
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Theory Theorist Rakhi Mahbubani Theorist Rakhi Mahbubani Theoretical physics at Fermilab Fermilab is a laboratory where advances in particle physics, astrophysics and cosmology converge. At Fermilab, theoretical physicists work hand-in-hand with experimenters. Theorists play a crucial role in making connections among the numerous discoveries made by experiments around the world each year. Accelerator-based experiments, for example, shed light on the fundamental particles and forces that have
Jack Shlachter presents Jews in Theory
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Jack Shlachter presents Jews in Theory Jack Shlachter presents Jews in Theory WHEN: Oct 04, 2015 3:00 PM - 4:00 PM WHERE: Bradbury Science Museum 1350 Central Ave, Los Alamos, NM...
Supplement to Theory of Neutron Chain Reactions
DOE R&D Accomplishments [OSTI]
Weinberg, Alvin M.; Noderer, L. C.
1952-05-26
General discussions are given of the theory of neutron chain reactions. These include observations on exponential experiments, the general reactor with resonance fission, microscopic pile theory, and homogeneous slow neutron reactors. (B.J.H.)
Three-point current correlation functions as probes of Effective Conformal
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Theories (Journal Article) | SciTech Connect SciTech Connect Search Results Journal Article: Three-point current correlation functions as probes of Effective Conformal Theories Citation Details In-Document Search Title: Three-point current correlation functions as probes of Effective Conformal Theories Authors: Betre, Kassahun ; /SLAC ; , Publication Date: 2013-11-11 OSTI Identifier: 1104714 Report Number(s): SLAC-PUB-15832 DOE Contract Number: AC02-76SF00515 Resource Type: Journal Article
1994 International Sherwood Fusion Theory Conference
1994-04-01
This report contains the abstracts of the paper presented at the 1994 International Sherwood Fusion Theory Conference.
Foundations of nonlinear gyrokinetic theory
Brizard, A. J.; Hahm, T. S.
2007-04-15
Nonlinear gyrokinetic equations play a fundamental role in our understanding of the long-time behavior of strongly magnetized plasmas. The foundations of modern nonlinear gyrokinetic theory are based on three pillars: (i) a gyrokinetic Vlasov equation written in terms of a gyrocenter Hamiltonian with quadratic low-frequency ponderomotivelike terms, (ii) a set of gyrokinetic Maxwell (Poisson-Ampere) equations written in terms of the gyrocenter Vlasov distribution that contain low-frequency polarization (Poisson) and magnetization (Ampere) terms, and (iii) an exact energy conservation law for the gyrokinetic Vlasov-Maxwell equations that includes all the relevant linear and nonlinear coupling terms. The foundations of nonlinear gyrokinetic theory are reviewed with an emphasis on rigorous application of Lagrangian and Hamiltonian Lie-transform perturbation methods in the variational derivation of nonlinear gyrokinetic Vlasov-Maxwell equations. The physical motivations and applications of the nonlinear gyrokinetic equations that describe the turbulent evolution of low-frequency electromagnetic fluctuations in a nonuniform magnetized plasmas with arbitrary magnetic geometry are discussed.
A new quasidilaton theory of massive gravity (Journal Article...
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A new quasidilaton theory of massive gravity Citation Details In-Document Search Title: A new quasidilaton theory of massive gravity We present a new quasidilaton theory of...
Renormalized linear kinetic theory as derived from quantum field...
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Renormalized linear kinetic theory as derived from quantum field theory: A novel ... Citation Details In-Document Search Title: Renormalized linear kinetic theory as derived ...
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Clay, Raymond C.; Holzmann, Markus; Ceperley, David M.; Morales, Maguel A.
2016-01-19
An accurate understanding of the phase diagram of dense hydrogen and helium mixtures is a crucial component in the construction of accurate models of Jupiter, Saturn, and Jovian extrasolar planets. Though DFT based rst principles methods have the potential to provide the accuracy and computational e ciency required for this task, recent benchmarking in hydrogen has shown that achieving this accuracy requires a judicious choice of functional, and a quanti cation of the errors introduced. In this work, we present a quantum Monte Carlo based benchmarking study of a wide range of density functionals for use in hydrogen-helium mixtures atmore » thermodynamic conditions relevant for Jovian planets. Not only do we continue our program of benchmarking energetics and pressures, but we deploy QMC based force estimators and use them to gain insights into how well the local liquid structure is captured by di erent density functionals. We nd that TPSS, BLYP and vdW-DF are the most accurate functionals by most metrics, and that the enthalpy, energy, and pressure errors are very well behaved as a function of helium concentration. Beyond this, we highlight and analyze the major error trends and relative di erences exhibited by the major classes of functionals, and estimate the magnitudes of these e ects when possible.« less
Saad, Yousef
2014-03-19
The master project under which this work is funded had as its main objective to develop computational methods for modeling electronic excited-state and optical properties of various nanostructures. The specific goals of the computer science group were primarily to develop effective numerical algorithms in Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TDDFT). There were essentially four distinct stated objectives. The first objective was to study and develop effective numerical algorithms for solving large eigenvalue problems such as those that arise in Density Functional Theory (DFT) methods. The second objective was to explore so-called linear scaling methods or Methods that avoid diagonalization. The third was to develop effective approaches for Time-Dependent DFT (TDDFT). Our fourth and final objective was to examine effective solution strategies for other problems in electronic excitations, such as the GW/Bethe-Salpeter method, and quantum transport problems.
Triangular flow in hydrodynamics and transport theory
Alver, Burak Han [Laboratory for Nuclear Science, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307 (United States); Gombeaud, Clement; Luzum, Matthew; Ollitrault, Jean-Yves [CNRS, URA2306, IPhT, Institut de physique theorique de Saclay, F-91191 Gif-sur-Yvette (France)
2010-09-15
In ultrarelativistic heavy-ion collisions, the Fourier decomposition of the relative azimuthal angle, {Delta}{phi}, distribution of particle pairs yields a large cos(3{Delta}{phi}) component, extending to large rapidity separations {Delta}{eta}>1. This component captures a significant portion of the ridge and shoulder structures in the {Delta}{phi} distribution, which have been observed after contributions from elliptic flow are subtracted. An average finite triangularity owing to event-by-event fluctuations in the initial matter distribution, followed by collective flow, naturally produces a cos(3{Delta}{phi}) correlation. Using ideal and viscous hydrodynamics and transport theory, we study the physics of triangular (v{sub 3}) flow in comparison to elliptic (v{sub 2}), quadrangular (v{sub 4}), and pentagonal (v{sub 5}) flow. We make quantitative predictions for v{sub 3} at RHIC and LHC as a function of centrality and transverse momentum. Our results for the centrality dependence of v{sub 3} show a quantitative agreement with data extracted from previous correlation measurements by the STAR collaboration. This study supports previous results on the importance of triangular flow in the understanding of ridge and shoulder structures. Triangular flow is found to be a sensitive probe of initial geometry fluctuations and viscosity.
Building a Universal Nuclear Energy Density Functional
Carlson, Joe A.; Furnstahl, Dick; Horoi, Mihai; Lust, Rusty; Nazaewicc, Witek; Ng, Esmond; Thompson, Ian; Vary, James
2012-12-30
During the period of Dec. 1 2006 – Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: First, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; Second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; Third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory.
Filtration theory using computer simulations
Bergman, W.; Corey, I.
1997-01-01
We have used commercially available fluid dynamics codes based on Navier-Stokes theory and the Langevin particle equation of motion to compute the particle capture efficiency and pressure drop through selected two- and three- dimensional fiber arrays. The approach we used was to first compute the air velocity vector field throughout a defined region containing the fiber matrix. The particle capture in the fiber matrix is then computed by superimposing the Langevin particle equation of motion over the flow velocity field. Using the Langevin equation combines the particle Brownian motion, inertia and interception mechanisms in a single equation. In contrast, most previous investigations treat the different capture mechanisms separately. We have computed the particle capture efficiency and the pressure drop through one, 2-D and two, 3-D fiber matrix elements.
Locally smeared operator product expansions in scalar field theory
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Monahan, Christopher; Orginos, Kostas
2015-04-01
We propose a new locally smeared operator product expansion to decompose non-local operators in terms of a basis of smeared operators. The smeared operator product expansion formally connects nonperturbative matrix elements determined numerically using lattice field theory to matrix elements of non-local operators in the continuum. These nonperturbative matrix elements do not suffer from power-divergent mixing on the lattice, which significantly complicates calculations of quantities such as the moments of parton distribution functions, provided the smearing scale is kept fixed in the continuum limit. The presence of this smearing scale complicates the connection to the Wilson coefficients of the standardmore » operator product expansion and requires the construction of a suitable formalism. We demonstrate the feasibility of our approach with examples in real scalar field theory.« less
The Theory of Variances in Equilibrium Reconstruction
Zakharov, Leonid E.; Lewandowski, Jerome; Foley, Elizabeth L.; Levinton, Fred M.; Yuh, Howard Y.; Drozdov, Vladimir; McDonald, Darren
2008-01-14
The theory of variances of equilibrium reconstruction is presented. It complements existing practices with information regarding what kind of plasma profiles can be reconstructed, how accurately, and what remains beyond the abilities of diagnostic systems. The #27;σ-curves, introduced by the present theory, give a quantitative assessment of quality of effectiveness of diagnostic systems in constraining equilibrium reconstructions. The theory also suggests a method for aligning the accuracy of measurements of different physical nature.
Unimodular theory: A little pedagogical vision
Fernndez Cristbal, Jose Ma
2014-11-15
Under the generic designation of unimodular theory, two theoretical models of gravity are considered: the unimodular gravity and the TDiff theory. Our approach is primarily pedagogical. We aim to describe these models both from a geometric and a field-theoretical point of view. In addition, we explore connections with the cosmological-constant problem and outline some applications. We do not discuss the application of this theory to the quantization of gravity.
Julian Schwinger and the Source Theory
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of elementary particles". "The theoretical achievements of Schwinger and Richard Feynman in the late 1940s and early 1950s ignited a revolution in quantum field theory and ...
MIT-CTP/4229 Effective Field Theory
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Field Theory of Fractional Quantized Hall Nematics Michael Mulligan, 1 Chetan Nayak, 2 and Shamit Kachru 3 1 Center for Theoretical Physics, MIT, Cambridge, MA 02139, USA 2...
NREL: Energy Sciences - Solid-State Theory
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Science Printable Version Solid-State Theory Image showing a roughly spherical red shape that looks like an apple that is floating within a yellow hemispherical shell....
A different Big Bang theory: Los Alamos
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different Big Bang theory: Los Alamos unveils explosives detection expertise February 11, 2015 Collaboration project defeats explosives threats through enhanced detection...
Extracting the Eliashberg Function
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Extracting the Eliashberg Function Extracting the Eliashberg Function Print Wednesday, 23 February 2005 00:00 A multitude of important chemical, physical, and biological phenomena...
Crystallization and functionality of inorganic materials
Xue, Dongfeng, E-mail: dongfeng@ciac.jl.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China) [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Li, Keyan [School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China)] [School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Liu, Jun [Key Laboratory of Low Dimensional Materials and Application Technology, Ministry of Education, Faculty of Materials, Optoelectronics and Physics, Xiangtan University, 411105 (China)] [Key Laboratory of Low Dimensional Materials and Application Technology, Ministry of Education, Faculty of Materials, Optoelectronics and Physics, Xiangtan University, 411105 (China); Sun, Congting; Chen, Kunfeng [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China) [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China)
2012-10-15
In this article, we briefly summarized our recent work on the studies of crystallization and functionality of inorganic materials. On the basis of the chemical bonding theory of single crystal growth, we can quantitatively simulate Cu{sub 2}O crystallization processes in solution system. We also kinetically controlled Cu{sub 2}O crystallization process in the reduction solution route. Lithium ion battery and supercapacitor performances of some oxides such as Co{sub 3}O{sub 4} and MnO{sub 2} were shown to elucidate the important effect of crystallization on functionality of inorganic materials. This work encourages us to create novel functionalities through the study of crystallization of inorganic materials, which warrants more chances in the field of functional materials.
Critical Assessment of Function Annotation Meeting, 2011
Friedberg, Iddo
2015-01-21
The Critical Assessment of Function Annotation meeting was held July 14-15, 2011 at the Austria Conference Center in Vienna, Austria. There were 73 registered delegates at the meeting. We thank the DOE for this award. It helped us organize and support a scientific meeting AFP 2011 as a special interest group (SIG) meeting associated with the ISMB 2011 conference. The conference was held in Vienna, Austria, in July 2011. The AFP SIG was held on July 15-16, 2011 (immediately preceding the conference). The meeting consisted of two components, the first being a series of talks (invited and contributed) and discussion sections dedicated to protein function research, with an emphasis on the theory and practice of computational methods utilized in functional annotation. The second component provided a large-scale assessment of computational methods through participation in the Critical Assessment of Functional Annotation (CAFA).
Renormalized linear kinetic theory as derived from quantum field theory: A
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novel diagrammatic method for computing transport coefficients (Journal Article) | SciTech Connect Renormalized linear kinetic theory as derived from quantum field theory: A novel diagrammatic method for computing transport coefficients Citation Details In-Document Search Title: Renormalized linear kinetic theory as derived from quantum field theory: A novel diagrammatic method for computing transport coefficients We propose a novel diagrammatic method for computing transport coefficients in
Magnetoelectroluminescence of organic heterostructures: Analytical theory
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and spectrally resolved measurements (Journal Article) | SciTech Connect Magnetoelectroluminescence of organic heterostructures: Analytical theory and spectrally resolved measurements Citation Details In-Document Search Title: Magnetoelectroluminescence of organic heterostructures: Analytical theory and spectrally resolved measurements The effect of a magnetic field on the electroluminescence of organic light emitting devices originates from the hyperfine interaction between the
Theory of multiphoton ionization of atoms
Szoeke, A.
1986-03-01
A non-perturbative approach to the theory of multiphoton ionization is reviewed. Adiabatic Floquet theory is its first approximation. It explains qualitatively the energy and angular distribution of photoelectrons. In many-electron atoms it predicts collective and inner shell excitation. 14 refs.
Analytical theory of multipass crystal extraction
Biryukov, V.; Murphy, C.T.
1997-10-01
An analytical theory for the efficiency of particle extraction from an accelerator by means of a bent crystal is proposed. The theory agrees with all the measurements performed in the broad energy range of 14 to 900 GeV, where the efficiency range also spans over two decades, from {approximately}0.3% to {approximately}30%.
Geometric Hamiltonian structures and perturbation theory
Omohundro, S.
1984-08-01
We have been engaged in a program of investigating the Hamiltonian structure of the various perturbation theories used in practice. We describe the geometry of a Hamiltonian structure for non-singular perturbation theory applied to Hamiltonian systems on symplectic manifolds and the connection with singular perturbation techniques based on the method of averaging.
Chemistry: Theory - Combustion Energy Frontier Research Center
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Theory Chemistry: Theory Presentations from 2010 CEFRC First Annual Conference MultireferenceCorrelated WavefunctionCalculations and Reaction Flux Analyses of Methyl Ester Combustion Emily A. Carter, Princeton University Constructing Accurate Combustion Chemistry Models William H. Green, MIT Theoretical Gas Phase Chemical Kinetics Stephen J. Klippenstein, Argonne National Laboratory Theoretical Chemical Kinetics and Combustion Modeling James A. Miller, Argonne National Laboratory Computation of
Molecular theory of fluid thermal properties
Tewari, K.P.; Zhang, S.; White, J.A.
1993-04-01
A recently developed renormalization group theory of condensable gases that takes into account short range attractive intermolecular forces is successful in describing the thermal properties of real fluids both at the critical point and in a large adjoining neighborhood. The theory has been tested for a variety of models, and for real gases such as argon and ethane. In its simplest form, the theory employs three free parameters - attraction constant a, hard core volume b, and cohesion volume c of the molecules. These parameters can be calculated from the theory and the authors have done so using Lennard-Jones and Yukawa potentials with hard cores. A brief review of the theory will be presented and results discussed.
Statistical theory of turbulent incompressible multimaterial flow
Kashiwa, B.
1987-10-01
Interpenetrating motion of incompressible materials is considered. ''Turbulence'' is defined as any deviation from the mean motion. Accordingly a nominally stationary fluid will exhibit turbulent fluctuations due to a single, slowly moving sphere. Mean conservation equations for interpenetrating materials in arbitrary proportions are derived using an ensemble averaging procedure, beginning with the exact equations of motion. The result is a set of conservation equations for the mean mass, momentum and fluctuational kinetic energy of each material. The equation system is at first unclosed due to integral terms involving unknown one-point and two-point probability distribution functions. In the mean momentum equation, the unclosed terms are clearly identified as representing two physical processes. One is transport of momentum by multimaterial Reynolds stresses, and the other is momentum exchange due to pressure fluctuations and viscous stress at material interfaces. Closure is approached by combining careful examination of multipoint statistical correlations with the traditional physical technique of kappa-epsilon modeling for single-material turbulence. This involves representing the multimaterial Reynolds stress for each material as a turbulent viscosity times the rate of strain based on the mean velocity of that material. The multimaterial turbulent viscosity is related to the fluctuational kinetic energy kappa, and the rate of fluctuational energy dissipation epsilon, for each material. Hence a set of kappa and epsilon equations must be solved, together with mean mass and momentum conservation equations, for each material. Both kappa and the turbulent viscosities enter into the momentum exchange force. The theory is applied to (a) calculation of the drag force on a sphere fixed in a uniform flow, (b) calculation of the settling rate in a suspension and (c) calculation of velocity profiles in the pneumatic transport of solid particles in a pipe.
Maurer, Simon A.; Clin, Lucien; Ochsenfeld, Christian
2014-06-14
Our recently developed QQR-type integral screening is introduced in our Cholesky-decomposed pseudo-densities Mller-Plesset perturbation theory of second order (CDD-MP2) method. We use the resolution-of-the-identity (RI) approximation in combination with efficient integral transformations employing sparse matrix multiplications. The RI-CDD-MP2 method shows an asymptotic cubic scaling behavior with system size and a small prefactor that results in an early crossover to conventional methods for both small and large basis sets. We also explore the use of local fitting approximations which allow to further reduce the scaling behavior for very large systems. The reliability of our method is demonstrated on test sets for interaction and reaction energies of medium sized systems and on a diverse selection from our own benchmark set for total energies of larger systems. Timings on DNA systems show that fast calculations for systems with more than 500 atoms are feasible using a single processor core. Parallelization extends the range of accessible system sizes on one computing node with multiple cores to more than 1000 atoms in a double-zeta basis and more than 500 atoms in a triple-zeta basis.
G Gainsford; G Evans; K Johnston; M Seth
2011-12-31
The title compound, abbreviated as 5'ThiomethylImmA, is a potent inhibitor of methylthioadenosine phosphorylase [Singh et al. (2004). Biochemistry, 43, 9-18]. The synchrotron study reported here shows that the hydrochloride salt crystallizes with two independent, nearly superimposable, dications as a monohydrate with formula 2C{sub 12}H{sub 19}N{sub 5}O{sub 2}S{sup 2+}{center_dot}4Cl{sup -}{center_dot}H{sub 2}O. Hydrogen bonding utilizing the H atoms of the dication is found to favor certain molecular conformations in the salt, which are significantly different from those found as bound in the enzyme. Ligand docking studies starting from either of these dications or related neutral structures successfully place the conformationally revised structures in the enzyme active site but only under particular hydrogen-bonding and molecular flexibility criteria. Density functional theory calculations verify the energy similarity of the indendent cations and confirm the significant energy cost of the required conformation change to the enzyme bound form. The results suggest the using crystallographically determined free ligand coordinates as starting parameters for modelling may have serious limitations.
Solvent Exchange in Liquid Methanol and Rate Theory
Dang, Liem X.; Schenter, Gregory K.
2016-01-01
To enhance our understanding of the solvent exchange mechanism in liquid methanol, we report a systematic study of this process using molecular dynamics simulations. We use transition state theory, the Impey-Madden-McDonald method, the reactive flux method, and Grote-Hynes theory to compute the rate constants for this process. Solvent coupling was found to dominate, resulting in a significantly small transmission coefficient. We predict a positive activation volume for the methanol exchange process. The essential features of the dynamics of the system as well as the pressure dependence are recovered from a Generalized Langevin Equation description of the dynamics. We find that the dynamics and response to anharmonicity can be decomposed into two time regimes, one corresponding to short time response (< 0.1 ps) and long time response (> 5 ps). An effective characterization of the process results from launching dynamics from the planar hypersurface corresponding to Grote-Hynes theory. This results in improved numerical convergence of correlation functions. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.
Hamiltonian Light-front Field Theory Within an AdS/QCD Basis
Vary, J.P.; Honkanen, H.; Li, Jun; Maris, P.; Brodsky, S.J.; Harindranath, A.; de Teramond, G.F.; Sternberg, P.; Ng, E.G.; Yang, C.; /LBL, Berkeley
2009-12-16
Non-perturbative Hamiltonian light-front quantum field theory presents opportunities and challenges that bridge particle physics and nuclear physics. Fundamental theories, such as Quantum Chromodynamics (QCD) and Quantum Electrodynamics (QED) offer the promise of great predictive power spanning phenomena on all scales from the microscopic to cosmic scales, but new tools that do not rely exclusively on perturbation theory are required to make connection from one scale to the next. We outline recent theoretical and computational progress to build these bridges and provide illustrative results for nuclear structure and quantum field theory. As our framework we choose light-front gauge and a basis function representation with two-dimensional harmonic oscillator basis for transverse modes that corresponds with eigensolutions of the soft-wall AdS/QCD model obtained from light-front holography.
Unraveling the Structure of Hadrons with Effective Field Theories of QCD
Iain Stewart
2004-06-08
Effective Field theory is a powerful framework based on controlled expansions for problems with a natural separation of energy scales. This technique is particularly important for QCD, the theory of strong interactions, due to the vast diversity of phenomena that it describes. Stewart and collaborators have invented a new class of effective theories that can be used in processes with energetic hadrons. These Soft-Collinear Effective Theories provide a unified framework for describing hadronic processes which involve hard probes or the release of a large amount of energy. Many interesting issues about hadronic physics can be addressed with the soft-collinear effective theory. Examples include the size and shape of hadronic form factors, the universality of hadronic distribution functions for a plethora of processes, and the importance of subleading corrections at intermediate energy scales. Effective field theories allow these issues to be addressed using only the underlying symmetries and scales in QCD. Understanding these issues also has a direct impact on other areas of physics, such as on devising clean methods for the measurement of CP violation in the decay of B-mesons. Current progress on the soft-collinear effective theory and related methods is discussed in this report.
Newell, Matthew R.
2012-05-16
The UNAP DCM board is capable of measuring currents with a dynamic range of 3 x 10{sup -14} A to 3 x 10{sup -4} A. The design of the DCM closely matches the proven N-1 minigrand family DCM design. The most significant difference is the replacement of the Actel FPGA with an SPI I/O expander. The original DCM design used an Actel FPGA to communicate with the processor over the expansion bus controling the DCM gain and filtering. The UNAP processor communicates with the UDA FPGA over the cPCI bus. The UNAP DCM control functions are accomplished in the UDA FPGA and communicated to the DCM board via an SPI bus.
Functionalized boron nitride nanotubes
Sainsbury, Toby; Ikuno, Takashi; Zettl, Alexander K
2014-04-22
A plasma treatment has been used to modify the surface of BNNTs. In one example, the surface of the BNNT has been modified using ammonia plasma to include amine functional groups. Amine functionalization allows BNNTs to be soluble in chloroform, which had not been possible previously. Further functionalization of amine-functionalized BNNTs with thiol-terminated organic molecules has also been demonstrated. Gold nanoparticles have been self-assembled at the surface of both amine- and thiol-functionalized boron nitride Nanotubes (BNNTs) in solution. This approach constitutes a basis for the preparation of highly functionalized BNNTs and for their utilization as nanoscale templates for assembly and integration with other nanoscale materials.
Chrissanthopoulos, A.; Jovari, P.; Kaban, I.; Gruner, S.; Kavetskyy, T.; Borc, J.; Wang, W.; Ren, J.; Chen, G.; Yannopoulos, S.N.
2012-08-15
We report an investigation of the structure and vibrational modes of Ge-In-S-AgI bulk glasses using X-ray diffraction, EXAFS spectroscopy, Reverse Monte-Carlo (RMC) modelling, Raman spectroscopy, and density functional theoretical (DFT) calculations. The combination of these techniques made it possible to elucidate the short- and medium-range structural order of these glasses. Data interpretation revealed that the AgI-free glass structure is composed of a network where GeS{sub 4/2} tetrahedra are linked with trigonal InS{sub 3/2} units; S{sub 3/2}Ge-GeS{sub 3/2} ethane-like species linked with InS{sub 4/2}{sup -} tetrahedra form sub-structures which are dispersed in the network structure. The addition of AgI into the Ge-In-S glassy matrix causes appreciable structural changes, enriching the Indium species with Iodine terminal atoms. The existence of trigonal species InS{sub 2/2}I and tetrahedral units InS{sub 3/2}I{sup -} and InS{sub 2/2}I{sub 2}{sup -} is compatible with the EXAFS and RMC analysis. Their vibrational properties (harmonic frequencies and Raman activities) calculated by DFT are in very good agreement with the experimental values determined by Raman spectroscopy. - Graphical abstract: Experiment (XRD, EXAFS, RMC, Raman scattering) and density functional calculations are employed to study the structure of AgI-doped Ge-In-S glasses. The role of mixed structural units as illustrated in the figure is elucidated. Highlights: Black-Right-Pointing-Pointer Doping Ge-In-S glasses with AgI causes significant changes in glass structure. Black-Right-Pointing-Pointer Experiment and DFT are combined to elucidate short- and medium-range structural order. Black-Right-Pointing-Pointer Indium atoms form both (InS{sub 4/2}){sup -} tetrahedra and InS{sub 3/2} planar triangles. Black-Right-Pointing-Pointer (InS{sub 4/2}){sup -} tetrahedra bond to (S{sub 3/2}Ge-GeS{sub 3/2}){sup 2+} ethane-like units forming neutral sub-structures. Black-Right-Pointing-Pointer Mixed chalcohalide species (InS{sub 3/2}I){sup -} offer vulnerable sites for the uptake of Ag{sup +}.
Development of ab initio techniques critical for future science-based explosives R&D.
Wixom, Ryan R.; Mattsson, Ann Elisabet
2013-10-01
Density Functional Theory (DFT) has emerged as an indispensable tool in materials research, since it can accurately predict properties of a wide variety of materials at both equilibrium and extreme conditions. However, for organic molecular crystal explosives, successful application of DFT has largely failed due to the inability of current exchange-correlation functionals to correctly describe intermolecular van der Waals' (vdWs) forces. Despite this, we have discovered that even with no treatment of vdWs bonding, the AM05 functional and DFT based molecular dynamics (MD) could be used to study the properties of molecular crystals under compression. We have used DFT-MD to predict the unreacted Hugoniots for PETN and HNS and validated the results by comparison with crystalline and porous experimental data. Since we are also interested in applying DFT methods to study the equilibrium volume properties of explosives, we studied the nature of the vdWs bonding in pursuit of creating a new DFT functional capable of accurately describing equilibrium bonding of molecular crystals. In this report we discuss our results for computing shock Hugoniots of molecular crystals and also what was learned about the nature of bonding in these materials.
Portable Special Function Routines
Energy Science and Technology Software Center (OSTI)
1992-02-27
SPECFUN is a collection of transportable FORTRAN subroutines and accompanying test drivers to evaluate certain special functions.
Towards a next theory of superconductivity
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Communications Office (505) 667-0471 Email "High magnetic-field measurements of doped copper-oxide superconductors are paving the way to a new theory of superconductivity," said...
A cosmological study in massive gravity theory
Pan, Supriya Chakraborty, Subenoy
2015-09-15
A detailed study of the various cosmological aspects in massive gravity theory has been presented in the present work. For the homogeneous and isotropic FLRW model, the deceleration parameter has been evaluated, and, it has been examined whether there is any transition from deceleration to acceleration in recent past, or not. With the proper choice of the free parameters, it has been shown that the massive gravity theory is equivalent to Einstein gravity with a modified Newtonian gravitational constant together with a negative cosmological constant. Also, in this context, it has been examined whether the emergent scenario is possible, or not, in massive gravity theory. Finally, we have done a cosmographic analysis in massive gravity theory.
Energy in the Einstein-aether theory
Eling, Christopher
2006-04-15
We investigate the energy of a theory with a unit vector field (the aether) coupled to gravity. Both the Weinberg and Einstein type energy-momentum pseudotensors are employed. In the linearized theory we find expressions for the energy density of the 5 wave modes. The requirement that the modes have positive energy is then used to constrain the theory. In the fully nonlinear theory we compute the total energy of an asymptotically flat spacetime. The resulting energy expression is modified by the presence of the aether due to the nonzero value of the unit vector at infinity and its 1/r falloff. The question of nonlinear energy positivity is also discussed, but not resolved.
1995 International Sherwood Fusion Theory Conference
1995-07-01
This book is a guide to the 1995 International Sherwood Fusion Theory Conference. It consists largely of abstracts of the oral and poster presentations that were to be made, and gives some general information about the conference and its schedule.
General Embedded Brane Effective Field Theories
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Goon, Garrett L.; Hinterbichler, Kurt; Trodden, Mark
2011-06-10
We presented a new general class of four-dimensional effective field theories with interesting global symmetry groups, which may prove relevant to the cosmology of both the early and late universe.
KAYENTA : theory and user's guide.
Brannon, Rebecca Moss; Fossum, Arlo Frederick; Strack, Otto Eric
2009-03-01
The physical foundations and domain of applicability of the Kayenta constitutive model are presented along with descriptions of the source code and user instructions. Kayenta, which is an outgrowth of the Sandia GeoModel, includes features and fitting functions appropriate to a broad class of materials including rocks, rock-like engineered materials (such as concretes and ceramics), and metals. Fundamentally, Kayenta is a computational framework for generalized plasticity models. As such, it includes a yield surface, but the term 'yield' is generalized to include any form of inelastic material response including microcrack growth and pore collapse. Kayenta supports optional anisotropic elasticity associated with ubiquitous joint sets. Kayenta supports optional deformation-induced anisotropy through kinematic hardening (in which the initially isotropic yield surface is permitted to translate in deviatoric stress space to model Bauschinger effects). The governing equations are otherwise isotropic. Because Kayenta is a unification and generalization of simpler models, it can be run using as few as 2 parameters (for linear elasticity) to as many as 40 material and control parameters in the exceptionally rare case when all features are used. For high-strain-rate applications, Kayenta supports rate dependence through an overstress model. Isotropic damage is modeled through loss of stiffness and strength.
KAYENTA: Theory and User's Guide
Brannon, Rebecca Moss; Fuller, Timothy Jesse; Strack, Otto Eric; Fossum, Arlo Frederick; Sanchez, Jason James
2015-02-01
The physical foundations and domain of applicability of the Kayenta constitutive model are presented along with descriptions of the source code and user instructions. Kayenta, which is an outgrowth of the Sandia GeoModel, includes features and fitting functions appropriate to a broad class of materials including rocks, rock-like engineered materials (such as concretes and ceramics), and metals. Fundamentally, Kayenta is a computational framework for generalized plasticity models. As such, it includes a yield surface, but the term (3z(Byield(3y (Bis generalized to include any form of inelastic material response (including microcrack growth and pore collapse) that can result in non-recovered strain upon removal of loads on a material element. Kayenta supports optional anisotropic elasticity associated with joint sets, as well as optional deformation-induced anisotropy through kinematic hardening (in which the initially isotropic yield surface is permitted to translate in deviatoric stress space to model Bauschinger effects). The governing equations are otherwise isotropic. Because Kayenta is a unification and generalization of simpler models, it can be run using as few as 2 parameters (for linear elasticity) to as many as 40 material and control parameters in the exceptionally rare case when all features are used. For high-strain-rate applications, Kayenta supports rate dependence through an overstress model. Isotropic damage is modeled through loss of stiffness and strength.
Perturbation theory in light-cone quantization
Langnau, A.
1992-01-01
A thorough investigation of light-cone properties which are characteristic for higher dimensions is very important. The easiest way of addressing these issues is by analyzing the perturbative structure of light-cone field theories first. Perturbative studies cannot be substituted for an analysis of problems related to a nonperturbative approach. However, in order to lay down groundwork for upcoming nonperturbative studies, it is indispensable to validate the renormalization methods at the perturbative level, i.e., to gain control over the perturbative treatment first. A clear understanding of divergences in perturbation theory, as well as their numerical treatment, is a necessary first step towards formulating such a program. The first objective of this dissertation is to clarify this issue, at least in second and fourth-order in perturbation theory. The work in this dissertation can provide guidance for the choice of counterterms in Discrete Light-Cone Quantization or the Tamm-Dancoff approach. A second objective of this work is the study of light-cone perturbation theory as a competitive tool for conducting perturbative Feynman diagram calculations. Feynman perturbation theory has become the most practical tool for computing cross sections in high energy physics and other physical properties of field theory. Although this standard covariant method has been applied to a great range of problems, computations beyond one-loop corrections are very difficult. Because of the algebraic complexity of the Feynman calculations in higher-order perturbation theory, it is desirable to automatize Feynman diagram calculations so that algebraic manipulation programs can carry out almost the entire calculation. This thesis presents a step in this direction. The technique we are elaborating on here is known as light-cone perturbation theory.
Jack Shlachter presents Jews in Theory
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Jack Shlachter presents Jews in Theory Jack Shlachter presents Jews in Theory WHEN: Oct 04, 2015 3:00 PM - 4:00 PM WHERE: Bradbury Science Museum 1350 Central Ave, Los Alamos, NM 87544 USA SPEAKER: Jack Shlachter, Acting Division Leader, Theoretical Division at Los Alamos National Laboratory CATEGORY: Bradbury INTERNAL: Calendar Login Jack Shlachter Event Description A special presentation about the history of Jews in Los Alamos National Laboratory's Theoretical Division. A snapshot of the
Alpha particles in effective field theory
Caniu, C.
2014-11-11
Using an effective field theory for alpha (?) particles at non-relativistic energies, we calculate the strong scattering amplitude modified by Coulomb corrections for a system of two ?s. For the strong interaction, we consider a momentum-dependent interaction which, in contrast to an energy dependent interaction alone [1], could be more useful in extending the theory to systems with more than two ? particles. We will present preliminary results of our EFT calculations for systems with two alpha particles.
Effective Theory of Chiral Superfluids and Superconductors
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Institute for Materials Science Seminar Effective Theory of Chiral Superfluids and Superconductors WHEN: Mar 24, 2016 9:00 AM - 1:00 PM WHERE: Hot Rocks Conference Room, TA-3, Bldg. 4200, Room 203-A SPEAKER: Sergej Moroz, Condensed Matter Theory Group, University of Colorado CONTACT: Caryll Blount (505) 665-3950 CATEGORY: Community Science TYPE: Seminar INTERNAL: Calendar Login Event Description Two-dimensional fermionic chiral superfluidity and superconductivity is an active area of
Electronic Structure Theory | Materials Science | NREL
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Electronic Structure Theory An image of multiple, interconnecting red and blue particles Using high-performance computing, NREL applies electronic structure theory to design and discover materials for energy applications. This includes detailed studies of the physical mechanisms that determine the material's behavior on an atomistic level. Learn more about high-performance computing. Key Research Areas Materials by Design NREL leads the U.S. Department of Energy's Center for Next Generation of
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Ward, B. F. L.
2008-01-01
We show that it is possible to improve the infrared aspects of the standard treatment of the DGLAP-CS evolution theory to take into account a large class of higher-order corrections that significantly improve the precision of the theory for any given level of fixed-order calculation of its respective kernels. We illustrate the size of the effects we resum using the moments of the parton distributions.
New Dualities in Supersymmetric Chiral Gauge Theories (Journal...
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When F N + 3 the theory flows to a superconformal fixed point in the infrared, and new dual descriptions of this theory are uncovered. The theory with odd N admits...
Universal Nuclear Energy Density Functional (Technical Report) | SciTech
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Connect Universal Nuclear Energy Density Functional Citation Details In-Document Search Title: Universal Nuclear Energy Density Functional An understanding of the properties of atomic nuclei is crucial for a complete nuclear theory, for element formation, for properties of stars, and for present and future energy and defense applications. During the period of Dec. 1 2006 - Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate
Determination of linear optics functions from TBT data
Alexahin, Y.; Gianfelice-Wendt, E.; /Fermilab
2006-05-01
A method for evaluation of coupled optics functions, detection of strong perturbing elements, determination of BPM calibration errors and tilts using turn-by-turn (TBT) data is presented as well as the new version of the Hamiltonian perturbation theory of betatron oscillations the method is based upon. An example of application of the considered method to the Tevatron is given.
Stochastic many-body perturbation theory for anharmonic molecular vibrations
Hermes, Matthew R.; Hirata, So
2014-08-28
A new quantum Monte Carlo (QMC) method for anharmonic vibrational zero-point energies and transition frequencies is developed, which combines the diagrammatic vibrational many-body perturbation theory based on the Dyson equation with Monte Carlo integration. The infinite sums of the diagrammatic and thus size-consistent first- and second-order anharmonic corrections to the energy and self-energy are expressed as sums of a few m- or 2m-dimensional integrals of wave functions and a potential energy surface (PES) (m is the vibrational degrees of freedom). Each of these integrals is computed as the integrand (including the value of the PES) divided by the value of a judiciously chosen weight function evaluated on demand at geometries distributed randomly but according to the weight function via the Metropolis algorithm. In this way, the method completely avoids cumbersome evaluation and storage of high-order force constants necessary in the original formulation of the vibrational perturbation theory; it furthermore allows even higher-order force constants essentially up to an infinite order to be taken into account in a scalable, memory-efficient algorithm. The diagrammatic contributions to the frequency-dependent self-energies that are stochastically evaluated at discrete frequencies can be reliably interpolated, allowing the self-consistent solutions to the Dyson equation to be obtained. This method, therefore, can compute directly and stochastically the transition frequencies of fundamentals and overtones as well as their relative intensities as pole strengths, without fixed-node errors that plague some QMC. It is shown that, for an identical PES, the new method reproduces the correct deterministic values of the energies and frequencies within a few cm{sup −1} and pole strengths within a few thousandths. With the values of a PES evaluated on the fly at random geometries, the new method captures a noticeably greater proportion of anharmonic effects.
Chiral effective field theory predictions for muon capture on...
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Journal Article: Chiral effective field theory predictions for muon capture on deuteron and 3He Citation Details In-Document Search Title: Chiral effective field theory...
Constraining PCP Violating Varying Alpha Theory through Laboratory...
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Constraining PCP Violating Varying Alpha Theory through Laboratory Experiments Citation Details In-Document Search Title: Constraining PCP Violating Varying Alpha Theory through ...
Application of Random Vibration Theory Methodology for Seismic...
Application of Random Vibration Theory Methodology for Seismic Soil-Structure Interaction Analysis Application of Random Vibration Theory Methodology for Seismic Soil-Structure...
Theory, modeling and evaluations for the fuel cycle (Conference...
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MaRIE theory, modeling and computation roadmap executive summary...
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Conference: MaRIE theory, modeling and computation roadmap executive summary Citation Details In-Document Search Title: MaRIE theory, modeling and computation roadmap executive ...
Combined local-density and dynamical mean field theory calculations...
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field theory calculations for the compressed lanthanides Ce, Pr, and Nd Citation Details In-Document Search Title: Combined local-density and dynamical mean field theory ...
Microscopic Theory of Fission (Conference) | SciTech Connect
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Microscopic Theory of Fission Citation Details In-Document Search Title: Microscopic Theory of Fission Authors: Younes, W ; Gogny, D Publication Date: 2008-01-03 OSTI Identifier: ...
Communication: The simplified generalized entropy theory of glass...
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Communication: The simplified generalized entropy theory of glass-formation in polymer ... Title: Communication: The simplified generalized entropy theory of glass-formation in ...
The Microscopic Theory of Fission (Conference) | SciTech Connect
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Conference: The Microscopic Theory of Fission Citation Details In-Document Search Title: The Microscopic Theory of Fission Fission-fragment properties have been calculated for ...
A Linear Theory of Microwave Instability in Electron Storage...
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Journal Article: A Linear Theory of Microwave Instability in Electron Storage Rings Citation Details In-Document Search Title: A Linear Theory of Microwave Instability in Electron ...
Neutron Production by Muon Spallation I: Theory (Technical Report...
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Neutron Production by Muon Spallation I: Theory Citation Details In-Document Search Title: Neutron Production by Muon Spallation I: Theory We describe the physics and codes ...
Effective Field Theory of Fractional Quantized Hall Nematics...
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The Effective Field Theory of Multifield Inflation (Journal Article...
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The Effective Field Theory of Multifield Inflation Citation Details In-Document Search Title: The Effective Field Theory of Multifield Inflation Authors: Senatore, Leonardo ; ...
Effective matrix model for deconfinement in pure gauge theories...
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Effective field theory of fractional quantized Hall nematics...
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Surface theory of a family of topological Kondo insulators (Journal...
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Surface theory of a family of topological Kondo insulators Prev Next Title: Surface theory of a family of topological Kondo insulators Authors: Roy, Bitan ; Sau, Jay D. ; ...
The Effective Field Theory of Dark Matter Direct Detection (Journal...
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Theory of factors limiting high gradient operation of warm acceleratin...
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A Linear Theory of Microwave Instability in Electron Storage...
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The Effective Field Theory of Dark Matter Direct Detection (Journal...
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The Effective Field Theory of Cosmological Large Scale Structures...
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Theory and Modeling of Weakly Bound/Physisorbed Materials for...
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Theory and Modeling of Weakly BoundPhysisorbed Materials for Hydrogen Storage Theory and Modeling of Weakly BoundPhysisorbed Materials for Hydrogen Storage Presentation on the...
Simulation and Theory of Ions at Atmospherically Relevant Aqueous...
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Local Three-Nucleon Interaction from Chiral Effective Field Theory...
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Disformal invariance of cosmological perturbations in a generalized class of Horndeski theories
Tsujikawa, Shinji
2015-04-27
It is known that Horndeski theories can be transformed to a sub-class of Gleyzes-Langlois-Piazza-Vernizzi (GLPV) theories under the disformal transformation of the metric g{sub μν}→Ω{sup 2}(ϕ)g{sub μν}+Γ(ϕ,X)∇{sub μ}ϕ∇{sub ν}ϕ, where Ω is a function of a scalar field ϕ and Γ is another function depending on both ϕ and X=g{sup μν}∇{sub μ}ϕ∇{sub ν}ϕ. We show that, with the choice of unitary gauge, both curvature and tensor perturbations on the flat isotropic cosmological background are generally invariant under the disformal transformation. By means of the effective field theories encompassing Horndeski and GLPV theories, we obtain the second-order actions of scalar/tensor perturbations and present the relations for physical quantities between the two frames. The invariance of the inflationary power spectra under the disformal transformation is explicitly proved up to next-to-leading order in slow-roll. In particular, we identify the existence of the Einstein frame in which the tensor power spectrum is of the same form as that in General Relativity and derive the condition under which the spectrum of gravitational waves in GLPV theories is red-tilted.
Geometric perturbation theory and plasma physics
Omohundro, S.M.
1985-04-04
Modern differential geometric techniques are used to unify the physical asymptotics underlying mechanics, wave theory and statistical mechanics. The approach gives new insights into the structure of physical theories and is suited to the needs of modern large-scale computer simulation and symbol manipulation systems. A coordinate-free formulation of non-singular perturbation theory is given, from which a new Hamiltonian perturbation structure is derived and related to the unperturbed structure. The theory of perturbations in the presence of symmetry is developed, and the method of averaging is related to reduction by a circle group action. The pseudo-forces and magnetic Poisson bracket terms due to reduction are given a natural asymptotic interpretation. Similar terms due to changing reference frames are related to the method of variation of parameters, which is also given a Hamiltonian formulation. These methods are used to answer a question about nearly periodic systems. The answer leads to a new secular perturbation theory that contains no ad hoc elements. Eikonal wave theory is given a Hamiltonian formulation that generalizes Whitham's Lagrangian approach. The evolution of wave action density on ray phase space is given a Hamiltonian structure using a Lie-Poisson bracket. The relationship between dissipative and Hamiltonian systems is discussed. A new type of attractor is defined which attracts both forward and backward in time and is shown to occur in infinite-dimensional Hamiltonian systems with dissipative behavior. The theory of Smale horseshoes is applied to gyromotion in the neighborhood of a magnetic field reversal and the phenomenon of reinsertion in area-preserving horseshoes is introduced. The central limit theorem is proved by renormalization group techniques. A natural symplectic structure for thermodynamics is shown to arise asymptotically from the maximum entropy formalism.
Bachhuber, Frederik; Krach, Alexander; Furtner, Andrea; Söhnel, Tilo; Peter, Philipp; Rothballer, Jan; Weihrich, Richard
2015-03-15
Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.
CASL - Mixing and non-stoichiometry in Fe-Ni-Cr-Zn-O spinel compounds:
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Density functional theory calculations Mixing and non-stoichiometry in Fe-Ni-Cr-Zn-O spinel compounds: Density functional theory calculations Mixing and non-stoichiometry in Fe-Ni-Cr-Zn-O spinel compounds: Density functional theory calculations D.A. Andersson and C.R. Stanek Materials Science and Technology Division Los Alamos National Laboratory Density functional theory (DFT) calculations have been employed to better understand the thermodynamic properties of AB2O4 (where A=Fe2+, Ni2+ or
Qin, Hong; Davidson, Ronald C.; Burby, Joshua W.; Chung, Moses
2014-04-08
The dynamics of charged particles in general linear focusing lattices with quadrupole, skew-quadrupole, dipole, and solenoidal components, as well as torsion of the fiducial orbit and variation of beam energy is parametrized using a generalized Courant-Snyder (CS) theory, which extends the original CS theory for one degree of freedom to higher dimensions. The envelope function is generalized into an envelope matrix, and the phase advance is generalized into a 4D symplectic rotation, or a U2 element. The 1D envelope equation, also known as the Ermakov-Milne-Pinney equation in quantum mechanics, is generalized to an envelope matrix equation in higher dimensions. Other components of the original CS theory, such as the transfer matrix, Twiss functions, and CS invariant (also known as the Lewis invariant) all have their counterparts, with remarkably similar expressions, in the generalized theory. The gauge group structure of the generalized theory is analyzed. By fixing the gauge freedom with a desired symmetry, the generalized CS parametrization assumes the form of the modified Iwasawa decomposition, whose importance in phase space optics and phase space quantum mechanics has been recently realized. This gauge fixing also symmetrizes the generalized envelope equation and expresses the theory using only the generalized Twiss function ?. The generalized phase advance completely determines the spectral and structural stability properties of a general focusing lattice. For structural stability, the generalized CS theory enables application of the Krein-Moser theory to greatly simplify the stability analysis. The generalized CS theory provides an effective tool to study coupled dynamics and to discover more optimized lattice designs in the larger parameter space of general focusing lattices.
Pohle, H.
1989-03-15
We investigate lambdaphi/sup 4/ theory within the Gaussian approximation in spatially flat Robertson-Walker space in 3+1 dimensions. After having performed an adiabatic expansion for one of the ansatz functions, we find that the renormalization of the energy-momentum tensor provides two additional constraints which have to be satisfied by the bare couplings. These conditions force the theory to be trivial after renormalization.
National Computational Infrastructure for Lattice Gauge Theory
Brower, Richard C.
2014-04-15
SciDAC-2 Project The Secret Life of Quarks: National Computational Infrastructure for Lattice Gauge Theory, from March 15, 2011 through March 14, 2012. The objective of this project is to construct the software needed to study quantum chromodynamics (QCD), the theory of the strong interactions of sub-atomic physics, and other strongly coupled gauge field theories anticipated to be of importance in the energy regime made accessible by the Large Hadron Collider (LHC). It builds upon the successful efforts of the SciDAC-1 project National Computational Infrastructure for Lattice Gauge Theory, in which a QCD Applications Programming Interface (QCD API) was developed that enables lattice gauge theorists to make effective use of a wide variety of massively parallel computers. This project serves the entire USQCD Collaboration, which consists of nearly all the high energy and nuclear physicists in the United States engaged in the numerical study of QCD and related strongly interacting quantum field theories. All software developed in it is publicly available, and can be downloaded from a link on the USQCD Collaboration web site, or directly from the github repositories with entrance linke http://usqcd-software.github.io
Weakly interacting two-dimensional system of dipoles: Limitations of the mean-field theory
Astrakharchik, G. E.; Boronat, J.; Casulleras, J.; Kurbakov, I. L.; Lozovik, Yu. E.
2007-06-15
We consider a homogeneous two-dimensional Bose gas with repulsive dipole-dipole interactions. The ground-state equation of state, calculated using the diffusion Monte Carlo method, shows quantitative differences from the predictions of the commonly used Gross-Pitaevskii mean-field theory. The static structure factor, pair distribution function, and condensate fraction are calculated in a wide range of the gas parameter. Differences from mean-field theory are reflected in the frequency of the lowest ''breathing'' mode for harmonically trapped systems.
Theory of RBE. Technical progress report
Katz, Robert
1983-08-01
Dye films and alanine are being studied for application as dosimetric substances in relation to track theory. The objective is to test track theory with dosimeters whose sensitive target is about one manometer in size. Results with the dye films give good agreement with a slightly modified track theory. Cellular radiosensitivity parameters have been fitted to inactivation data obtained with particles up to neon, in the grain-count regime, and then returning to the basic model of a single on-target detector to calculate the track width regime. A new model has been created for the formation of etchable tracks in plastics. The model is consistent with some published data for CR-39, and suggest this material is another 1-hit detector. (ACR)
Neutron stars in Einstein-aether theory
Eling, Christopher; Jacobson, Ted; Miller, M. Coleman
2007-08-15
As current and future experiments probe strong gravitational regimes around neutron stars and black holes, it is desirable to have theoretically sound alternatives to general relativity against which to test observations. Here we study the consequences of one such generalization, Einstein-aether theory, for the properties of nonrotating neutron stars. This theory has a parameter range that satisfies all current weak-field tests. We find that within this range it leads to lower maximum neutron star masses, as well as larger surface redshifts at a particular mass, for a given nuclear equation of state. For nonrotating black holes and neutron stars, the innermost stable circular orbit is only slightly modified in this theory.
Berkolaiko, G.; Kuipers, J.
2013-12-15
Electronic transport through chaotic quantum dots exhibits universal behaviour which can be understood through the semiclassical approximation. Within the approximation, calculation of transport moments reduces to codifying classical correlations between scattering trajectories. These can be represented as ribbon graphs and we develop an algorithmic combinatorial method to generate all such graphs with a given genus. This provides an expansion of the linear transport moments for systems both with and without time reversal symmetry. The computational implementation is then able to progress several orders further than previous semiclassical formulae as well as those derived from an asymptotic expansion of random matrix results. The patterns observed also suggest a general form for the higher orders.
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Principles Simulation and Model-Driven Isotopic Labeling Experiments Reveal Biomass Decomposition Pathways 1 Theory driven experimental confirmation Intensity (arb. units) 600 550 500 450 400 350 300 250 Temperature (K) H 2 (2amu) background DOCH 2 CH 2 OD HOCD 2 CD 2 OH 398K 322K 346K 432K (A) * Density functional theory (DFT) calculations of ethylene glycol decomposition on Pt(111) and Ni/Pt(111) reveal key differences between decomposition of highly functionalized oxygenates compared to
Metric redefinitions in Einstein-Aether theory
Foster, Brendan Z.
2005-08-15
'Einstein-Aether' theory, in which gravity couples to a dynamical, timelike, unit-norm vector field, provides a means for studying Lorentz violation in a generally covariant setting. Demonstrated here is the effect of a redefinition of the metric and 'aether' fields in terms of the original fields and two free parameters. The net effect is a change of the coupling constants appearing in the action. Using such a redefinition, one of the coupling constants can be set to zero, simplifying studies of solutions of the theory.
Extreme neutron stars from Extended Theories of Gravity
Astashenok, Artyom V.; Capozziello, Salvatore; Odintsov, Sergei D. E-mail: capozziello@na.infn.it
2015-01-01
We discuss neutron stars with strong magnetic mean fields in the framework of Extended Theories of Gravity. In particular, we take into account models derived from f(R) and f(G) extensions of General Relativity where functions of the Ricci curvature invariant R and the Gauss-Bonnet invariant G are respectively considered. Dense matter in magnetic mean field, generated by magnetic properties of particles, is described by assuming a model with three meson fields and baryons octet. As result, the considerable increasing of maximal mass of neutron stars can be achieved by cubic corrections in f(R) gravity. In principle, massive stars with M>4M{sub ?} can be obtained. On the other hand, stable stars with high strangeness fraction (with central densities ?{sub c}?1.52.0 GeV/fm{sup 3}) are possible considering quadratic corrections of f(G) gravity. The magnetic field strength in the star center is of order 68נ10{sup 18} G. In general, we can say that other branches of massive neutron stars are possible considering the extra pressure contributions coming from gravity extensions. Such a feature can constitute both a probe for alternative theories and a way out to address anomalous self-gravitating compact systems.
Resizing the conformal window: A {beta}-function ansatz
Antipin, O.; Tuominen, K.
2010-04-01
We propose an ansatz for the nonperturbative beta-function of a generic nonsupersymmetric Yang-Mills theory with or without fermions in an arbitrary representation of the gauge group. While our construction is similar to the recently proposed Ryttov-Sannino all-order beta-function, the essential difference is that it allows for the existence of an unstable ultraviolet fixed point in addition to the predicted Banks-Zaks-like infrared stable fixed point. Our beta-function preserves all of the tested features with respect to the nonsupersymmetric Yang-Mills theories. We predict the conformal window identifying the lower end of it as a merger of the infrared and ultraviolet fixed points.
Energy Science and Technology Software Center (OSTI)
2015-05-26
Octopus is a scientific program aimed at the ab initio virtual experimentation on a hopefully ever-increasing range of system types. Electrons are described quantum-mechanically within density-functional theory (DFT), in its time-dependent form (TDDFT) when doing simulations in time. Nuclei are described classically as point particles. Electron-nucleus interaction is described within the pseudopotential approximation.
Ivana Adamovic
2004-12-19
This dissertation consists of two closely related parts: theory development and coding of correlation effects in a model potential for solvation, and study of solvent effects on chemical reactions and processes. The effective fragment potential (EFP) method has been re-parameterized, using density functional theory (DFT), more specifically, the B3LYP functional. The DFT based EFP method includes short-range correlation effects; hence it is a first step in incorporating the treatment of correlation in the EFP solvation model. In addition, the gradient of the charge penetration term in the EFP model was derived and coded. The new method has been implemented in the electronic structure code GAMESS and is in use. Formulas for the dynamic dipole polarizability, C{sub 6} dispersion coefficient and dispersion energy were derived and coded as a part of a treatment of the dispersion interactions in the general solvation model, EFP2. Preliminary results are in good agreement with experimental and other theoretical data. The DFT based EFP (EFP1/DFT) method was used in the study of microsolvation effects on the S{sub N}2 substitution reaction, between chloride and methyl bromide. Changes in the central barrier, for several lowest lying isomers of the systems with one, two, three and four waters, were studied using second order perturbation theory (MP2), DFT and mixed quantum mechanics (QM)/(EFP1/DFT) methods. EFP1/DFT is found to reproduce QM results with high accuracy, at just a fraction of the cost. Molecular structures and potential energy surfaces for IHI{sup -} {center_dot} Ar{sub n} (n=1-7) were studied using the MP2 method. Experimentally observed trends in the structural arrangement of the Ar atoms were explained through the analysis of the geometrical parameters and three-dimensional MP2 molecular electrostatic potentials.
Explicit Expressions for 3D Boundary Integrals in Potential Theory
Nintcheu Fata, Sylvain
2009-01-01
On employing isoparametric, piecewise linear shape functions over a flat triangular domain, exact expressions are derived for all surface potentials involved in the numerical solution of three-dimensional singular and hyper-singular boundary integral equations of potential theory. These formulae, which are valid for an arbitrary source point in space, are represented as analytic expressions over the edges of the integration triangle. They can be used to solve integral equations defined on polygonal boundaries via the collocation method or may be utilized as analytic expressions for the inner integrals in the Galerkin technique. Also, the constant element approximation can be directly obtained with no extra effort. Sample problems solved by the collocation boundary element method for the Laplace equation are included to validate the proposed formulae.
Breaking discrete symmetries in the effective field theory of inflation
Cannone, Dario; Gong, Jinn-Ouk; Tasinato, Gianmassimo
2015-08-03
We study the phenomenon of discrete symmetry breaking during the inflationary epoch, using a model-independent approach based on the effective field theory of inflation. We work in a context where both time reparameterization symmetry and spatial diffeomorphism invariance can be broken during inflation. We determine the leading derivative operators in the quadratic action for fluctuations that break parity and time-reversal. Within suitable approximations, we study their consequences for the dynamics of linearized fluctuations. Both in the scalar and tensor sectors, we show that such operators can lead to new direction-dependent phases for the modes involved. They do not affect the power spectra, but can have consequences for higher correlation functions. Moreover, a small quadrupole contribution to the sound speed can be generated.
Extended Horava gravity and Einstein-aether theory
Jacobson, Ted
2010-05-15
Einstein-aether theory is general relativity coupled to a dynamical, unit timelike vector. If this vector is restricted in the action to be hypersurface orthogonal, the theory is identical to the IR limit of the extension of Horava gravity proposed by Blas, Pujolas and Sibiryakov. Hypersurface orthogonal solutions of Einstein-aether theory are solutions to the IR limit of this theory, hence numerous results already obtained for Einstein-aether theory carry over.
Fundamentals of the relativistic theory of gravitation
Logunov, A.A.; Mestvirishvili, M.A.
1986-01-01
An extended exposition of the relativistic theory of gravitation (RTG) proposed by Logunov, Vlasov, and Mestvirishvili is presented. The RTG was constructed uniquely on the basis of the relativity principle and the geometrization principle by regarding the gravitational field as a physical field in the spirit of Faraday and Maxwell possessing energy, momentum, and spins 2 and 0. In the theory, conservation laws for the energy, momentum, and angular momentum for the matter and gravitational field taken together are strictly satisfied. The theory explains all the existing gravitational experiments. When the evolution of the universe is analyzed, the theory leads to the conclusion that the universe is infinite and flat, and it is predicted to contain a large amount of hidden mass. This missing mass exceeds by almost 40 times the amount of matter currently observed in the universe. The RTG predicts that gravitational collapse, which for a comoving observer occurs after a finite proper time, does not lead to infinite compression of matter but is halted at a certain finite density of the collapsing body. Therefore, according to the RTG there cannot be any objects in nature in which the gravitational contraction of matter to infinite density occurs, i.e., there are no black holes.
Prequantum Classical Statistical Field Theory: Fundamentals
Khrennikov, Andrei
2011-03-28
We present fundamentals of a prequantum model with hidden variables of the classical field type. In some sense this is the comeback of classical wave mechanics. Our approach also can be considered as incorporation of quantum mechanics into classical signal theory. All quantum averages (including correlations of entangled systems) can be represented as classical signal averages and correlations.
Functionalized expanded porphyrins
Sessler, Jonathan L; Pantos, Patricia J
2013-11-12
Disclosed are functionalized expanded porphyrins that can be used as spectrometric sensors for high-valent actinide cations. The disclosed functionalized expanded porphyrins have the advantage over unfunctionalized systems in that they can be immobilized via covalent attachment to a solid support comprising an inorganic or organic polymer or other common substrates. Substrates comprising the disclosed functionalized expanded porphyrins are also disclosed. Further, disclosed are methods of making the disclosed compounds (immobilized and free), methods of using them as sensors to detect high valent actinides, devices that comprise the disclosed compounds, and kits.
Communication: Water on hexagonal boron nitride from diffusion Monte Carlo
Al-Hamdani, Yasmine S.; Ma, Ming; Michaelides, Angelos; Alf, Dario; Lilienfeld, O. Anatole von
2015-05-14
Despite a recent flurry of experimental and simulation studies, an accurate estimate of the interaction strength of water molecules with hexagonal boron nitride is lacking. Here, we report quantum Monte Carlo results for the adsorption of a water monomer on a periodic hexagonal boron nitride sheet, which yield a water monomer interaction energy of ?84 5 meV. We use the results to evaluate the performance of several widely used density functional theory (DFT) exchange correlation functionals and find that they all deviate substantially. Differences in interaction energies between different adsorption sites are however better reproduced by DFT.
Catti, Michele; Pinus, Ilya; Scherillo, Antonella
2013-09-15
First-principles quantum-mechanical calculations (CRYSTAL09 code, B3LYP functional) were performed on alkali titanates A{sub 2}Ti{sub n}O{sub 2n+1} with layered structure (n=3,4,6). Monoclinic structural types with unshifted (P2{sub 1}/m) and with shifted (C2/m) layers were considered. Crystal energies and full structural details were obtained for all Li, Na, and K phases. Neutron diffraction data were collected on powder samples of P2{sub 1}/m-Li{sub 2}Ti{sub 3}O{sub 7} (a=9.3146(3), b=3.7522(1), c=7.5447(3) Å, β=97.611(4)°) and C2/m-K{sub 2}Ti{sub 4}O{sub 9} (a=18.2578(8), b=3.79160(9), c=12.0242(4) Å, β=106.459(4)°) and their structures were Rietveld-refined. Computed energies show the P2{sub 1}/m arrangement as favoured over the C2/m one for n=3, and the opposite holds for n=6. In the n=4 case the P2{sub 1}/m configuration is predicted to be more stable for Li and Na, and the C2/m one for K titanates. Analysis of Li–O and K–O crystal-chemical environments from experiment and theory shows that the alkali atom bonding is stabilized/destabilized in the different phases consistently with the energy trend. - Graphical abstract: Display Omitted - Highlights: • The P2{sub 1}/m structure-type is found to be more stable for A{sub 2}Ti{sub 3}O{sub 7} layer titanates. • The C2/m structure-type is found to be more stable for A{sub 2}Ti{sub 6}O{sub 13} layer titanates. • Tetratitanates are predicted to prefer the P2{sub 1}/m (Li and Na) or C2/m (K) structure. • Li–O and K–O bond distances follow a trend consistent with computed phase energies.
Implausibility of the vibrational theory of olfaction
Block, Eric; Ertem, Mehmed Z.; Jang, Seogjoo; Matsunami, Hiroaki; Sekharan, Sivakumar; Dethier, Berenice; Gundala, Sivaji; Pan, Yi; Li, Shengju; Li, Zhen; Lodge, Stephene N.; Ozbil, Mehmet; Jiang, Huihong; Penalba, Sonia Flores; Batista, Victor S.; Zhuang, Hanyi
2015-04-21
The vibrational theory of olfaction assumes that electron transfer occurs across odorants at the active sites of odorant receptors (ORs), serving as a sensitive measure of odorant vibrational frequencies, ultimately leading to olfactory perception. A previous study reported that human subjects differentiated hydrogen/deuterium isotopomers (isomers with isotopic atoms) of the musk compound cyclopentadecanone as evidence supporting the theory. Here, we find no evidence for such differentiation at the molecular level. In fact, we find that the human musk-recognizing receptor, OR5AN1, identified using a heterologous OR expression system and robustly responding to cyclopentadecanone and muscone, fails to distinguish isotopomers of these compounds in vitro. Furthermore, the mouse (methylthio)methanethiol (MTMT)-recognizing receptor, MOR244-3, and other selected human and mouse ORs, responded similarly to normal, deuterated, and ¹³C isotopomers of their respective ligands, paralleling our results with the musk receptor OR5AN1. These findings suggest that the proposed vibration theory does not apply to the human musk receptor OR5AN1, mouse thiol receptor MOR244-3, or other ORs examined. Also, contrary to the vibration theory predictions, muscone-d₃₀ lacks the 1,380-1,550 cm⁻¹ IR bands claimed to be essential for musk odor. Furthermore, our theoretical analysis shows that the proposed electron transfer mechanism of the vibrational frequencies of odorants could be easily suppressed by quantum effects of non-odorant molecular vibrational modes. As a result, these and other concerns about electron transfer at ORs, together with our extensive experimental data, argue against the plausibility of the vibration theory.
Geometric Gyrokinetic Theory for Edge Plasma
Qin, H; Cohen, R H; Nevins, W M; Xu, X Q
2007-01-18
It turns out that gyrokinetic theory can be geometrically formulated as special cases of a geometrically generalized Vlasov-Maxwell system. It is proposed that the phase space of the spacetime is a 7-dimensional fiber bundle P over the 4-dimensional spacetime M, and that a Poincare-Cartan-Einstein 1-form {gamma} on the 7-dimensional phase space determines particles worldlines in the phase space. Through Liouville 6-form {Omega} and fiber integral, the 1-form {gamma} also uniquely defines a geometrically generalized Vlasov-Maxwell system as a field theory for the collective electromagnetic field. The geometric gyrokinetic theory is then developed as a special case of the geometrically generalized Vlasov-Maxwell system. In its most general form, gyrokinetic theory is about a symmetry, called gyro-symmetry, for magnetized plasmas, and the 1-form {gamma} again uniquely defines the gyro-symmetry. The objective is to decouple the gyro-phase dynamics from the rest of particle dynamics by finding the gyro-symmetry in {gamma}. Compared with other methods of deriving the gyrokinetic equations, the advantage of the geometric approach is that it allows any approximation based on mathematical simplification or physical intuition to be made at the 1-form level, and yet the field theories still have the desirable exact conservation properties such as phase space volume conservation and energy-momentum conservation if the 1-form does not depend on the spacetime coordinate explicitly. A set of generalized gyrokinetic equations valid for the edge plasmas is then derived using this geometric method. This formalism allows large-amplitude, time-dependent background electromagnetic fields to be developed fully nonlinearly in addition to small-amplitude, short-wavelength electromagnetic perturbations. The fact that we adopted the geometric method in the present study does not necessarily imply that the major results reported here can not be achieved using classical methods. What the geometric method offers is a systematic treatment and simplified calculations.
Implausibility of the vibrational theory of olfaction
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Block, Eric; Ertem, Mehmed Z.; Jang, Seogjoo; Matsunami, Hiroaki; Sekharan, Sivakumar; Dethier, Berenice; Gundala, Sivaji; Pan, Yi; Li, Shengju; Li, Zhen; et al
2015-04-21
The vibrational theory of olfaction assumes that electron transfer occurs across odorants at the active sites of odorant receptors (ORs), serving as a sensitive measure of odorant vibrational frequencies, ultimately leading to olfactory perception. A previous study reported that human subjects differentiated hydrogen/deuterium isotopomers (isomers with isotopic atoms) of the musk compound cyclopentadecanone as evidence supporting the theory. Here, we find no evidence for such differentiation at the molecular level. In fact, we find that the human musk-recognizing receptor, OR5AN1, identified using a heterologous OR expression system and robustly responding to cyclopentadecanone and muscone, fails to distinguish isotopomers of thesemore » compounds in vitro. Furthermore, the mouse (methylthio)methanethiol (MTMT)-recognizing receptor, MOR244-3, and other selected human and mouse ORs, responded similarly to normal, deuterated, and ¹³C isotopomers of their respective ligands, paralleling our results with the musk receptor OR5AN1. These findings suggest that the proposed vibration theory does not apply to the human musk receptor OR5AN1, mouse thiol receptor MOR244-3, or other ORs examined. Also, contrary to the vibration theory predictions, muscone-d₃₀ lacks the 1,380-1,550 cm⁻¹ IR bands claimed to be essential for musk odor. Furthermore, our theoretical analysis shows that the proposed electron transfer mechanism of the vibrational frequencies of odorants could be easily suppressed by quantum effects of non-odorant molecular vibrational modes. As a result, these and other concerns about electron transfer at ORs, together with our extensive experimental data, argue against the plausibility of the vibration theory.« less
Ghobadi, Ahmadreza F.; Elliott, J. Richard
2014-07-14
In this work, a new classical density functional theory is developed for group-contribution equations of state (EOS). Details of implementation are demonstrated for the recently-developed SAFT-? WCA EOS and selective applications are studied for confined fluids and vapor-liquid interfaces. The acronym WCA (Weeks-Chandler-Andersen) refers to the characterization of the reference part of the third-order thermodynamic perturbation theory applied in formulating the EOS. SAFT-? refers to the particular form of statistical associating fluid theory that is applied to the fused-sphere, heteronuclear, united-atom molecular models of interest. For the monomer term, the modified fundamental measure theory is extended to WCA-spheres. A new chain functional is also introduced for fused and soft heteronuclear chains. The attractive interactions are taken into account by considering the structure of the fluid, thus elevating the theory beyond the mean field approximation. The fluctuations of energy are also included via a non-local third-order perturbation theory. The theory includes resolution of the density profiles of individual groups such as CH{sub 2} and CH{sub 3} and satisfies stoichiometric constraints for the density profiles. New molecular simulations are conducted to demonstrate the accuracy of each Helmholtz free energy contribution in reproducing the microstructure of inhomogeneous systems at the united-atom level of coarse graining. At each stage, comparisons are made to assess where the present theory stands relative to the current state of the art for studying inhomogeneous fluids. Overall, it is shown that the characteristic features of real molecular fluids are captured both qualitatively and quantitatively. For example, the average pore density deviates ?2% from simulation data for attractive pentadecane in a 2-nm slit pore. Another example is the surface tension of ethane/heptane mixture, which deviates ?1% from simulation data while the theory reproduces the excess accumulation of ethane at the interface.
Extracting the Eliashberg Function
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Extracting the Eliashberg Function Extracting the Eliashberg Function Print Wednesday, 23 February 2005 00:00 A multitude of important chemical, physical, and biological phenomena are driven by violations of the Born-Oppenheimer approximation (BOA), which decouples electronic from nuclear motion in quantum calculations of solids. Recent advances in experimental techniques combined with ever-growing theoretical capabilities now hold the promise of presenting an unprecedented picture of these
Center for Functional Nanomaterials
BNL
2009-09-01
Staff from Brookhaven's new Center for Functional Nanomaterials (CFN) describe how this advanced facility will focus on the development and understanding of nanoscale materials. The CFN provides state-of-the-art capabilities for the fabrication and study of nanoscale materials, with an emphasis on atomic-level tailoring to achieve desired properties and functions. The overarching scientific theme of the CFN is the development and understanding of nanoscale materials that address the Nation's challenges in energy security.
McGraw, John T.; Zimmer, Peter C.; Ackermann, Mark R.
2012-01-24
Methods and apparatus for a structure function monitor provide for generation of parameters characterizing a refractive medium. In an embodiment, a structure function monitor acquires images of a pupil plane and an image plane and, from these images, retrieves the phase over an aperture, unwraps the retrieved phase, and analyzes the unwrapped retrieved phase. In an embodiment, analysis yields atmospheric parameters measured at spatial scales from zero to the diameter of a telescope used to collect light from a source.
Chiu Juiyu; Fuhrer, Andreas; Kelley, Randall; Manohar, Aneesh V.
2009-11-01
Previous work on electroweak radiative corrections to high-energy scattering using soft-collinear effective theory (SCET) has been extended to include external transverse and longitudinal gauge bosons and Higgs bosons. This allows one to compute radiative corrections to all parton-level hard scattering amplitudes in the standard model to next-to-leading-log order, including QCD and electroweak radiative corrections, mass effects, and Higgs exchange corrections, if the high-scale matching, which is suppressed by two orders in the log counting, and contains no large logs, is known. The factorization structure of the effective theory places strong constraints on the form of gauge theory amplitudes at high energy for massless and massive gauge theories, which are discussed in detail in the paper. The radiative corrections can be written as the sum of process-independent one-particle collinear functions, and a universal soft function. We give plots for the radiative corrections to qq{yields}W{sub T}W{sub T}, Z{sub T}Z{sub T}, W{sub L}W{sub L}, and Z{sub L}H, and gg{yields}W{sub T}W{sub T} to illustrate our results. The purely electroweak corrections are large, ranging from 12% at 500 GeV to 37% at 2 TeV for transverse W pair production, and increasing rapidly with energy. The estimated theoretical uncertainty to the partonic (hard) cross section in most cases is below 1%, smaller than uncertainties in the parton distribution functions. We discuss the relation between SCET and other factorization methods, and derive the Magnea-Sterman equations for the Sudakov form factor using SCET, for massless and massive gauge theories, and for light and heavy external particles.
A general theory of interference fringes in x-ray phase grating imaging
Yan, Aimin; Wu, Xizeng E-mail: liu@ou.edu; Liu, Hong E-mail: liu@ou.edu
2015-06-15
Purpose: The authors note that the concept of the Talbot self-image distance in x-ray phase grating interferometry is indeed not well defined for polychromatic x-rays, because both the grating phase shift and the fractional Talbot distances are all x-ray wavelength-dependent. For x-ray interferometry optimization, there is a need for a quantitative theory that is able to predict if a good intensity modulation is attainable at a given grating-to-detector distance. In this work, the authors set out to meet this need. Methods: In order to apply Fourier analysis directly to the intensity fringe patterns of two-dimensional and one-dimensional phase grating interferometers, the authors start their derivation from a general phase space theory of x-ray phase-contrast imaging. Unlike previous Fourier analyses, the authors evolved the Wigner distribution to obtain closed-form expressions of the Fourier coefficients of the intensity fringes for any grating-to-detector distance, even if it is not a fractional Talbot distance. Results: The developed theory determines the visibility of any diffraction order as a function of the grating-to-detector distance, the phase shift of the grating, and the x-ray spectrum. The authors demonstrate that the visibilities of diffraction orders can serve as the indicators of the underlying interference intensity modulation. Applying the theory to the conventional and inverse geometry configurations of single-grating interferometers, the authors demonstrated that the proposed theory provides a quantitative tool for the grating interferometer optimization with or without the Talbot-distance constraints. Conclusions: In this work, the authors developed a novel theory of the interference intensity fringes in phase grating x-ray interferometry. This theory provides a quantitative tool in design optimization of phase grating x-ray interferometers.
Theory & Computation > Research > The Energy Materials Center at Cornell
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Theory & Computation In This Section Computation & Simulation Theory & Computation Computation & Simulation
Estimating Terrorist Risk with Possibility Theory
J.L. Darby
2004-11-30
This report summarizes techniques that use possibility theory to estimate the risk of terrorist acts. These techniques were developed under the sponsorship of the Department of Homeland Security (DHS) as part of the National Infrastructure Simulation Analysis Center (NISAC) project. The techniques have been used to estimate the risk of various terrorist scenarios to support NISAC analyses during 2004. The techniques are based on the Logic Evolved Decision (LED) methodology developed over the past few years by Terry Bott and Steve Eisenhawer at LANL. [LED] The LED methodology involves the use of fuzzy sets, possibility theory, and approximate reasoning. LED captures the uncertainty due to vagueness and imprecision that is inherent in the fidelity of the information available for terrorist acts; probability theory cannot capture these uncertainties. This report does not address the philosophy supporting the development of nonprobabilistic approaches, and it does not discuss possibility theory in detail. The references provide a detailed discussion of these subjects. [Shafer] [Klir and Yuan] [Dubois and Prade] Suffice to say that these approaches were developed to address types of uncertainty that cannot be addressed by a probability measure. An earlier report discussed in detail the problems with using a probability measure to evaluate terrorist risk. [Darby Methodology]. Two related techniques are discussed in this report: (1) a numerical technique, and (2) a linguistic technique. The numerical technique uses traditional possibility theory applied to crisp sets, while the linguistic technique applies possibility theory to fuzzy sets. Both of these techniques as applied to terrorist risk for NISAC applications are implemented in software called PossibleRisk. The techniques implemented in PossibleRisk were developed specifically for use in estimating terrorist risk for the NISAC program. The LEDTools code can be used to perform the same linguistic evaluation as performed in PossibleRisk. [LEDTools] LEDTools is a general purpose linguistic evaluation tool and allows user defined universes of discourse and approximate reasoning rules, whereas PossibleRisk uses predefined universes of discourse (risk, attack, success, loss, and consequence) and rules. Also LEDTools has the capability to model a large number of threat scenarios with a graph and to integrate the scenarios (paths from the graph) into the linguistic evaluation. Example uses of PossibleRisk and LEDTools for the possibilistic evaluation of terrorist risk are provided in this report.
Alfred Stadler, Franz Gross
2010-10-01
We provide a short overview of the Covariant Spectator Theory and its applications. The basic ideas are introduced through the example of a {phi}{sup 4}-type theory. High-precision models of the two-nucleon interaction are presented and the results of their use in calculations of properties of the two- and three-nucleon systems are discussed. A short summary of applications of this framework to other few-body systems is also presented.
Local representation of the electronic dielectric response function
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Lu, Deyu; Ge, Xiaochuan
2015-12-11
We present a local representation of the electronic dielectric response function, based on a spatial partition of the dielectric response into contributions from each occupied Wannier orbital using a generalized density functional perturbation theory. This procedure is fully ab initio, and therefore allows us to rigorously define local metrics, such as “bond polarizability,” on Wannier centers. We show that the locality of the bare response function is determined by the locality of three quantities: Wannier functions of the occupied manifold, the density matrix, and the Hamiltonian matrix. Furthermore, in systems with a gap, the bare dielectric response is exponentially localized,more » which supports the physical picture of the dielectric response function as a collection of interacting local responses that can be captured by a tight-binding model.« less
Local representation of the electronic dielectric response function
Lu, Deyu; Ge, Xiaochuan
2015-12-11
We present a local representation of the electronic dielectric response function, based on a spatial partition of the dielectric response into contributions from each occupied Wannier orbital using a generalized density functional perturbation theory. This procedure is fully ab initio, and therefore allows us to rigorously define local metrics, such as bond polarizability, on Wannier centers. We show that the locality of the bare response function is determined by the locality of three quantities: Wannier functions of the occupied manifold, the density matrix, and the Hamiltonian matrix. Furthermore, in systems with a gap, the bare dielectric response is exponentially localized, which supports the physical picture of the dielectric response function as a collection of interacting local responses that can be captured by a tight-binding model.
Exploring theory space with Monte Carlo reweighting
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Gainer, James S.; Lykken, Joseph; Matchev, Konstantin T.; Mrenna, Stephen; Park, Myeonghun
2014-10-13
Theories of new physics often involve a large number of unknown parameters which need to be scanned. Additionally, a putative signal in a particular channel may be due to a variety of distinct models of new physics. This makes experimental attempts to constrain the parameter space of motivated new physics models with a high degree of generality quite challenging. We describe how the reweighting of events may allow this challenge to be met, as fully simulated Monte Carlo samples generated for arbitrary benchmark models can be effectively re-used. In particular, we suggest procedures that allow more efficient collaboration between theoristsmoreand experimentalists in exploring large theory parameter spaces in a rigorous way at the LHC.less
On partially massless theory in 3 dimensions
Alexandrov, Sergei; Deffayet, Cédric
2015-03-24
We analyze the first-order formulation of the ghost-free bigravity model in three-dimensions known as zwei-dreibein gravity. For a special choice of parameters, it was argued to have an additional gauge symmetry and give rise to a partially massless theory. We provide a thorough canonical analysis and identify that whether the theory becomes partially massless depends on the form of the stability condition of the secondary constraint responsible for the absence of the ghost. Generically, it is found to be an equation for a Lagrange multiplier implying that partially massless zwei-dreibein gravity does not exist. However, for special backgrounds this condition is identically satisfied leading to the presence of additional symmetries, which however disappear at quadratic order in perturbations.
Exploring theory space with Monte Carlo reweighting
Gainer, James S.; Lykken, Joseph; Matchev, Konstantin T.; Mrenna, Stephen; Park, Myeonghun
2014-10-13
Theories of new physics often involve a large number of unknown parameters which need to be scanned. Additionally, a putative signal in a particular channel may be due to a variety of distinct models of new physics. This makes experimental attempts to constrain the parameter space of motivated new physics models with a high degree of generality quite challenging. We describe how the reweighting of events may allow this challenge to be met, as fully simulated Monte Carlo samples generated for arbitrary benchmark models can be effectively re-used. Specifically, we suggest procedures that allow more efficient collaboration between theorists and experimentalists in exploring large theory parameter spaces in a rigorous way at the LHC.
Working Group Report: Lattice Field Theory
Blum, T.; et al.,
2013-10-22
This is the report of the Computing Frontier working group on Lattice Field Theory prepared for the proceedings of the 2013 Community Summer Study ("Snowmass"). We present the future computing needs and plans of the U.S. lattice gauge theory community and argue that continued support of the U.S. (and worldwide) lattice-QCD effort is essential to fully capitalize on the enormous investment in the high-energy physics experimental program. We first summarize the dramatic progress of numerical lattice-QCD simulations in the past decade, with some emphasis on calculations carried out under the auspices of the U.S. Lattice-QCD Collaboration, and describe a broad program of lattice-QCD calculations that will be relevant for future experiments at the intensity and energy frontiers. We then present details of the computational hardware and software resources needed to undertake these calculations.
Neutralino dark matter in BMSSM effective theory
Berg, Marcus; Edsj, Joakim; Lundstrm, Erik; Sjrs, Stefan; Gondolo, Paolo E-mail: edsjo@physto.se E-mail: erik@physto.se
2009-08-01
We study thermal neutralino dark matter in an effective field theory extension of the MSSM, called ''Beyond the MSSM'' (BMSSM) in Dine, Seiberg and Thomas (2007). In this class of effective field theories, the field content of the MSSM is unchanged, but the little hierarchy problem is alleviated by allowing small corrections to the Higgs/higgsino part of the Lagrangian. We perform parameter scans and compute the dark matter relic density. The light higgsino LSP scenario is modified the most; we find new regions of parameter space compared to the standard MSSM. This involves interesting interplay between the WMAP dark matter bounds and the LEP chargino bound. We also find some changes for gaugino LSPs, partly due to annihilation through a Higgs resonance, and partly due to coannihilation with light top squarks in models that are ruled in by the new effective terms.
Thermodynamics in variable speed of light theories
Racker, Juan [CONICET, Centro Atomico Bariloche, Avenida Bustillo 9500 (8400), San Carlos De Bariloche (Argentina); Facultad de Ciencias Astronomicas y Geofisicas, Universidad Nacional de La Plata, Paseo del Bosque S/N (1900), La Plata (Argentina); Sisterna, Pablo [Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Funes 3350 (7600), Mar del Plata (Argentina); Vucetich, Hector [Facultad de Ciencias Astronomicas y Geofisicas, Universidad Nacional de La Plata, Paseo del Bosque S/N (1900), La Plata (Argentina)
2009-10-15
The perfect fluid in the context of a covariant variable speed of light theory proposed by J. Magueijo is studied. On the one hand the modified first law of thermodynamics together with a recipe to obtain equations of state are obtained. On the other hand the Newtonian limit is performed to obtain the nonrelativistic hydrostatic equilibrium equation for the theory. The results obtained are used to determine the time variation of the radius of Mercury induced by the variability of the speed of light (c), and the scalar contribution to the luminosity of white dwarfs. Using a bound for the change of that radius and combining it with an upper limit for the variation of the fine structure constant, a bound on the time variation of c is set. An independent bound is obtained from luminosity estimates for Stein 2015B.
Exploring theory space with Monte Carlo reweighting
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Gainer, James S.; Lykken, Joseph; Matchev, Konstantin T.; Mrenna, Stephen; Park, Myeonghun
2014-10-13
Theories of new physics often involve a large number of unknown parameters which need to be scanned. Additionally, a putative signal in a particular channel may be due to a variety of distinct models of new physics. This makes experimental attempts to constrain the parameter space of motivated new physics models with a high degree of generality quite challenging. We describe how the reweighting of events may allow this challenge to be met, as fully simulated Monte Carlo samples generated for arbitrary benchmark models can be effectively re-used. Specifically, we suggest procedures that allow more efficient collaboration between theorists andmore » experimentalists in exploring large theory parameter spaces in a rigorous way at the LHC.« less
Can MONDian vector theories explain the cosmic speed up?
Cardone, Vincenzo F.; Radicella, Ninfa
2009-09-15
Generalized Einstein-Aether vector field models have been shown to provide, in the weak field regime, modifications to gravity which can be reconciled with the successful modified Newtonian dynamics (MOND) proposal. Very little is known, however, on the function F(K) defining the vector field Lagrangian so that an analysis of the viability of such theories at the cosmological scales has never been performed. As a first step along this route, we rely on the relation between F(K) and the MOND interpolating function {mu}(a/a{sub 0}) to assign the vector field Lagrangian thus obtaining what we refer to as MONDian vector models. Since they are able by construction to recover the MOND successes on galaxy scales, we investigate whether they can also drive the observed accelerated expansion by fitting the models to the type Ia supernovae data. Should this be the case, we have a unified framework where both dark energy and dark matter can be seen as different manifestations of a single vector field. It turns out that both MONDian vector models are able to well fit the low redshift data on type Ia supernovae, while some tension could be present in the high z regime.
Siegert pseudostate formulation of scattering theory: Two-channel case
Sitnikov, George V.; Tolstikhin, Oleg I.
2003-03-01
Siegert pseudostates (SPS) are a finite basis representation of Siegert states (SS) for finite-range potentials. This paper presents a generalization of the SPS formulation of scattering theory, originally developed by Tolstikhin, Ostrovsky, and Nakamura [Phys. Rev. A 58, 2077 (1998)] for s-wave scattering in the one-channel case, to s-wave scattering in the two-channel case. This includes the investigation of the properties of orthogonality and completeness of two-channel SPS and the derivation of the SPS expansions for the two-channel Green function, wave function, and scattering matrix. Similar to the one-channel case, two types of expansions for the scattering matrix are obtained: one has a form of a sum and requires the knowledge of both the SPS eigenvalues and eigenfunctions, while the other has a form of a product and involves the eigenvalues only. As the size of the basis tends to infinity, the product formulas obtained here in terms of SPS coincide with those given by Le Couteur [Proc. R. Soc. London, Ser. A 256, 115 (1960)] in terms of SS; all the other relations, as far as we know, have no counterparts in the literature. Partial widths of resonances in the case when both channels are open for decay are identified in terms of SPS - a feature that is absent in the one-channel case. The results are illustrated by numerical calculations for two model potentials.
Photovoltaic Theory and Modeling - Energy Innovation Portal
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Photovoltaic Theory and Modeling Los Alamos National Laboratory Contact LANL About This Technology Effect of Ligands on semiconductor QD DOS (quantum chemistry calculations) Effect of Ligands on semiconductor QD DOS (quantum chemistry calculations) Technology Marketing SummaryThe scientists developing this capability welcome the opportunity to unite with industry and advance its potential.DescriptionAs the solar industry works to build the infrastructure necessary to make electricity from
A different Big Bang theory: Los Alamos
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
different Big Bang theory: Los Alamos unveils explosives detection expertise February 11, 2015 Collaboration project defeats explosives threats through enhanced detection technologies LOS ALAMOS, N.M., Feb. 11, 2015-Having long kept details of its explosives capabilities under wraps, a team of Los Alamos National Laboratory scientists is now rolling out a collaborative project to defeat explosives threats through enhanced detection technologies. "We're aiming to create a collaboration of
Obstacle to populating the string theory landscape
Johnson, Matthew C; Larfors, Magdalena
2008-12-15
We construct domain walls and instantons in a class of models with coupled scalar fields, determining, in agreement with previous studies, that many such solutions contain naked timelike singularities. Vacuum bubble solutions of this type do not contain a region of true vacuum, obstructing the ability of eternal inflation to populate other vacua. We determine a criterion that potentials must satisfy to avoid the existence of such singularities and show that many domain wall solutions in type IIB string theory are singular.
Empirical Validation Workshop: Need and Theory
gov Empirical Validation Workshop: Need and Theory, Jan 28-29, 2015 Model vs Measured Pre-normative work by Labs, IEA, ASHRAE etc. becomes... Normative ANSI/ASHRAE Standard 140 Software Testing & Diagnostic Method: Finding needles in haystacks (BESTEST) 2 IRS & RESNET Qualified Software BESTESTed with Standard 140 EnerSim 179D Commercial Building Tax Credits (13 Simulation Tools) Hourly Analysis Program (HAP) RESNET (HERS, IECC, Tax Credits)(6 Tools) EnergyInsights(tm) TRANE/TRACE
Theory, Modeling and Simulation Annual Report 2000
Dixon, David A; Garrett, Bruce C; Straatsma, TP; Jones, Donald R; Studham, Scott; Harrison, Robert J; Nichols, Jeffrey A
2001-11-01
This annual report describes the 2000 research accomplishments for the Theory, Modeling, and Simulation (TM and S) directorate, one of the six research organizations in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). EMSL is a U.S. Department of Energy (DOE) national scientific user facility and is the centerpiece of the DOE commitment to providing world-class experimental, theoretical, and computational capabilities for solving the nation's environmental problems.
Theory, Modeling and Simulation Annual Report 2000
Dixon, David A.; Garrett, Bruce C.; Straatsma, Tp; Jones, Donald R.; Studham, Ronald S.; Harrison, Robert J.; Nichols, Jeffrey A.
2001-11-01
This annual report describes the 2000 research accomplishments for the Theory, Modeling, and Simulation (TM&S) directorate, one of the six research organizations in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) at Pacific Northwest National Laboratory (PNNL). EMSL is a U.S. Department of Energy (DOE) national scientific user facility and is the centerpiece of the DOE commitment to providing world-class experimental, theoretical, and computational capabilities for solving the nation's environmental problems.
Algal functional annotation tool
Lopez, D.; Casero, D.; Cokus, S. J.; Merchant, S. S.; Pellegrini, M.
2012-07-01
The Algal Functional Annotation Tool is a web-based comprehensive analysis suite integrating annotation data from several pathway, ontology, and protein family databases. The current version provides annotation for the model alga Chlamydomonas reinhardtii, and in the future will include additional genomes. The site allows users to interpret large gene lists by identifying associated functional terms, and their enrichment. Additionally, expression data for several experimental conditions were compiled and analyzed to provide an expression-based enrichment search. A tool to search for functionally-related genes based on gene expression across these conditions is also provided. Other features include dynamic visualization of genes on KEGG pathway maps and batch gene identifier conversion.
Radiation damping in Einstein-aether theory
Foster, Brendan Z.
2006-05-15
This work concerns the loss of energy of a material system due to gravitational radiation in Einstein-aether theory - an alternative theory of gravity in which the metric couples to a dynamical, timelike, unit-norm vector field. Derived to lowest post-Newtonian order are wave forms for the metric and vector fields far from a nearly Newtonian system and the rate of energy radiated by the system. The expressions depend on the quadrupole moment of the source, as in standard general relativity, but also contain monopolar and dipolar terms. There exists a one-parameter family of Einstein-aether theories for which only the quadrupolar contribution is present, and for which the expression for the damping rate is identical to that of general relativity to the order worked to here. This family cannot yet be declared observationally viable, since effects due to the strong internal fields of bodies in the actual systems used to test the damping rate have not yet been determined.
Adaptive multiconfigurational wave functions
Evangelista, Francesco A.
2014-03-28
A method is suggested to build simple multiconfigurational wave functions specified uniquely by an energy cutoff ?. These are constructed from a model space containing determinants with energy relative to that of the most stable determinant no greater than ?. The resulting ?-CI wave function is adaptive, being able to represent both single-reference and multireference electronic states. We also consider a more compact wave function parameterization (?+SD-CI), which is based on a small ?-CI reference and adds a selection of all the singly and doubly excited determinants generated from it. We report two heuristic algorithms to build ?-CI wave functions. The first is based on an approximate prescreening of the full configuration interaction space, while the second performs a breadth-first search coupled with pruning. The ?-CI and ?+SD-CI approaches are used to compute the dissociation curve of N{sub 2} and the potential energy curves for the first three singlet states of C{sub 2}. Special attention is paid to the issue of energy discontinuities caused by changes in the size of the ?-CI wave function along the potential energy curve. This problem is shown to be solvable by smoothing the matrix elements of the Hamiltonian. Our last example, involving the Cu{sub 2}O{sub 2}{sup 2+} core, illustrates an alternative use of the ?-CI method: as a tool to both estimate the multireference character of a wave function and to create a compact model space to be used in subsequent high-level multireference coupled cluster computations.
GADRAS Detector Response Function.
Mitchell, Dean J.; Harding, Lee; Thoreson, Gregory G; Horne, Steven M.
2014-11-01
The Gamma Detector Response and Analysis Software (GADRAS) applies a Detector Response Function (DRF) to compute the output of gamma-ray and neutron detectors when they are exposed to radiation sources. The DRF is fundamental to the ability to perform forward calculations (i.e., computation of the response of a detector to a known source), as well as the ability to analyze spectra to deduce the types and quantities of radioactive material to which the detectors are exposed. This document describes how gamma-ray spectra are computed and the significance of response function parameters that define characteristics of particular detectors.
Algal functional annotation tool
Energy Science and Technology Software Center (OSTI)
2012-07-12
Abstract BACKGROUND: Progress in genome sequencing is proceeding at an exponential pace, and several new algal genomes are becoming available every year. One of the challenges facing the community is the association of protein sequences encoded in the genomes with biological function. While most genome assembly projects generate annotations for predicted protein sequences, they are usually limited and integrate functional terms from a limited number of databases. Another challenge is the use of annotations tomore » interpret large lists of 'interesting' genes generated by genome-scale datasets. Previously, these gene lists had to be analyzed across several independent biological databases, often on a gene-by-gene basis. In contrast, several annotation databases, such as DAVID, integrate data from multiple functional databases and reveal underlying biological themes of large gene lists. While several such databases have been constructed for animals, none is currently available for the study of algae. Due to renewed interest in algae as potential sources of biofuels and the emergence of multiple algal genome sequences, a significant need has arisen for such a database to process the growing compendiums of algal genomic data. DESCRIPTION: The Algal Functional Annotation Tool is a web-based comprehensive analysis suite integrating annotation data from several pathway, ontology, and protein family databases. The current version provides annotation for the model alga Chlamydomonas reinhardtii, and in the future will include additional genomes. The site allows users to interpret large gene lists by identifying associated functional terms, and their enrichment. Additionally, expression data for several experimental conditions were compiled and analyzed to provide an expression-based enrichment search. A tool to search for functionally-related genes based on gene expression across these conditions is also provided. Other features include dynamic visualization of genes on KEGG pathway maps and batch gene identifier conversion. CONCLUSIONS: The Algal Functional Annotation Tool aims to provide an integrated data-mining environment for algal genomics by combining data from multiple annotation databases into a centralized tool. This site is designed to expedite the process of functional annotation and the interpretation of gene lists, such as those derived from high-throughput RNA-seq experiments. The tool is publicly available at http://pathways.mcdb.ucla.edu.« less
Algal functional annotation tool
2012-07-12
Abstract BACKGROUND: Progress in genome sequencing is proceeding at an exponential pace, and several new algal genomes are becoming available every year. One of the challenges facing the community is the association of protein sequences encoded in the genomes with biological function. While most genome assembly projects generate annotations for predicted protein sequences, they are usually limited and integrate functional terms from a limited number of databases. Another challenge is the use of annotations to interpret large lists of 'interesting' genes generated by genome-scale datasets. Previously, these gene lists had to be analyzed across several independent biological databases, often on a gene-by-gene basis. In contrast, several annotation databases, such as DAVID, integrate data from multiple functional databases and reveal underlying biological themes of large gene lists. While several such databases have been constructed for animals, none is currently available for the study of algae. Due to renewed interest in algae as potential sources of biofuels and the emergence of multiple algal genome sequences, a significant need has arisen for such a database to process the growing compendiums of algal genomic data. DESCRIPTION: The Algal Functional Annotation Tool is a web-based comprehensive analysis suite integrating annotation data from several pathway, ontology, and protein family databases. The current version provides annotation for the model alga Chlamydomonas reinhardtii, and in the future will include additional genomes. The site allows users to interpret large gene lists by identifying associated functional terms, and their enrichment. Additionally, expression data for several experimental conditions were compiled and analyzed to provide an expression-based enrichment search. A tool to search for functionally-related genes based on gene expression across these conditions is also provided. Other features include dynamic visualization of genes on KEGG pathway maps and batch gene identifier conversion. CONCLUSIONS: The Algal Functional Annotation Tool aims to provide an integrated data-mining environment for algal genomics by combining data from multiple annotation databases into a centralized tool. This site is designed to expedite the process of functional annotation and the interpretation of gene lists, such as those derived from high-throughput RNA-seq experiments. The tool is publicly available at http://pathways.mcdb.ucla.edu.
The viscosity to entropy ratio: From string theory motivated bounds to warm dense matter
Faussurier, G.; Libby, S. B.; Silvestrelli, P. L.
2014-07-04
Here, we study the ratio of viscosity to entropy density in Yukawa one-component plasmas as a function of coupling parameter at fixed screening, and in realistic warm dense matter models as a function of temperature at fixed density. In these two situations, the ratio is minimized for values of the coupling parameters that depend on screening, and for temperatures that in turn depend on density and material. In this context, we also examine Rosenfeld arguments relating transport coefficients to excess reduced entropy for Yukawa one-component plasmas. For these cases we show that this ratio is always above the lower-bound conjecture derived from string theory ideas.
Process for functionalizing alkanes
Bergman, R.G.; Janowicz, A.H.; Periana, R.A.
1988-05-24
Process for functionalizing saturated hydrocarbons comprises: (a) reacting said saturated hydrocarbons of the formula: R[sub 1]H wherein H represents a hydrogen atom; and R[sub 1] represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R[sub 2])[sub 3
On a theory of stability for nonlinear stochastic chemical reaction networks
Smadbeck, Patrick; Kaznessis, Yiannis N.
2015-05-14
We present elements of a stability theory for small, stochastic, nonlinear chemical reaction networks. Steady state probability distributions are computed with zero-information (ZI) closure, a closure algorithm that solves chemical master equations of small arbitrary nonlinear reactions. Stochastic models can be linearized around the steady state with ZI-closure, and the eigenvalues of the Jacobian matrix can be readily computed. Eigenvalues govern the relaxation of fluctuation autocorrelation functions at steady state. Autocorrelation functions reveal the time scales of phenomena underlying the dynamics of nonlinear reaction networks. In accord with the fluctuation-dissipation theorem, these functions are found to be congruent to response functions to small perturbations. Significant differences are observed in the stability of nonlinear reacting systems between deterministic and stochastic modeling formalisms.
Large N (=3) Neutrinos and Random Matrix Theory (Journal Article...
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Journal Article: Large N (3) Neutrinos and Random Matrix Theory Citation Details In-Document Search Title: Large N (3) Neutrinos and Random Matrix Theory You are accessing a ...
Theory of Fano Resonances in Graphene: The Kondo effect probed...
Office of Scientific and Technical Information (OSTI)
Journal Article: Theory of Fano Resonances in Graphene: The Kondo effect probed by STM Citation Details In-Document Search Title: Theory of Fano Resonances in Graphene: The Kondo ...
Theory of Fano Resonances in Graphene: The Kondo effect probed...
Office of Scientific and Technical Information (OSTI)
Theory of Fano Resonances in Graphene: The Kondo effect probed by STM Citation Details In-Document Search Title: Theory of Fano Resonances in Graphene: The Kondo effect probed by ...
Heavy Quarks, QCD, and Effective Field Theory (Technical Report...
Office of Scientific and Technical Information (OSTI)
Heavy Quarks, QCD, and Effective Field Theory Citation Details In-Document Search Title: Heavy Quarks, QCD, and Effective Field Theory The research supported by this OJI award is ...
Soft Collinear Effective Theory (Journal Article) | SciTech Connect
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Soft Collinear Effective Theory Citation Details In-Document Search Title: Soft Collinear Effective Theory In this talk I review soft collinear effective theory. After a discussion of the formalism and properties of the effective field theory, I turn to phenomenology. I present results on color-suppressed B {yields} D decays, and on the {upsilon} radiative decay spectrum. Authors: Fleming, Sean [1] + Show Author Affiliations Physics Department, University of Arizona, Tucson, AZ 85719 (United
Effective Field Theory of Fractional Quantized Hall Nematics (Journal
Office of Scientific and Technical Information (OSTI)
Article) | SciTech Connect Effective Field Theory of Fractional Quantized Hall Nematics Citation Details In-Document Search Title: Effective Field Theory of Fractional Quantized Hall Nematics We present a Landau-Ginzburg theory for a fractional quantized Hall nematic state and the transition to it from an isotropic fractional quantum Hall state. This justifies Lifshitz-Chern-Simons theory - which is shown to be its dual - on a more microscopic basis and enables us to compute a ground state
DOE Theory Focus Session on Hydrogen Storage Materials
Broader source: Energy.gov [DOE]
This agenda provides information about the DOE Theory Focus Session on Hydrogen Storage Materials on May 18, 2006.
Theory, modeling and simulation: Annual report 1993
Dunning, T.H. Jr.; Garrett, B.C.
1994-07-01
Developing the knowledge base needed to address the environmental restoration issues of the US Department of Energy requires a fundamental understanding of molecules and their interactions in insolation and in liquids, on surfaces, and at interfaces. To meet these needs, the PNL has established the Environmental and Molecular Sciences Laboratory (EMSL) and will soon begin construction of a new, collaborative research facility devoted to advancing the understanding of environmental molecular science. Research in the Theory, Modeling, and Simulation program (TMS), which is one of seven research directorates in the EMSL, will play a critical role in understanding molecular processes important in restoring DOE`s research, development and production sites, including understanding the migration and reactions of contaminants in soils and groundwater, the development of separation process for isolation of pollutants, the development of improved materials for waste storage, understanding the enzymatic reactions involved in the biodegradation of contaminants, and understanding the interaction of hazardous chemicals with living organisms. The research objectives of the TMS program are to apply available techniques to study fundamental molecular processes involved in natural and contaminated systems; to extend current techniques to treat molecular systems of future importance and to develop techniques for addressing problems that are computationally intractable at present; to apply molecular modeling techniques to simulate molecular processes occurring in the multispecies, multiphase systems characteristic of natural and polluted environments; and to extend current molecular modeling techniques to treat complex molecular systems and to improve the reliability and accuracy of such simulations. The program contains three research activities: Molecular Theory/Modeling, Solid State Theory, and Biomolecular Modeling/Simulation. Extended abstracts are presented for 89 studies.
Molecular theory and the effects of solute attractive forces on hydrophobic interactions
Chaudhari, Mangesh I.; Rempe, Susan B.; Asthagiri, D.; Tan, L.; Pratt, L. R.
2015-12-22
The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. We present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar–Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are opposite in sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasichemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar–Ar rdfs permit evaluation of osmotic second virial coefficients B_{2}. Those B_{2}’s also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, B_{2} can change from positive to negative values with increasing temperatures. Furthermore, this is consistent with the puzzling suggestions of decades ago that B_{2} ≈ 0 for intermediate cases of temperature or solute size. In all cases here, B_{2} becomes more attractive with increasing temperature.
Molecular theory and the effects of solute attractive forces on hydrophobic interactions
DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)
Chaudhari, Mangesh I.; Rempe, Susan B.; Asthagiri, D.; Tan, L.; Pratt, L. R.
2015-12-22
The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. We present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar–Ar rdfs considered pointwise, the numerical results for themore » effects of solute attractive forces on hydrophobic interactions are opposite in sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasichemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar–Ar rdfs permit evaluation of osmotic second virial coefficients B2. Those B2’s also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, B2 can change from positive to negative values with increasing temperatures. Furthermore, this is consistent with the puzzling suggestions of decades ago that B2 ≈ 0 for intermediate cases of temperature or solute size. In all cases here, B2 becomes more attractive with increasing temperature.« less
Process for functionalizing alkanes
Bergman, R.G.; Janowicz, A.H.; Periana-Pillai, R.A.
1984-06-12
Process for functionalizing saturated hydrocarbons selectively in the terminal position comprises: (a) reacting said saturated hydrocarbons with a metal complex CpRhPMe/sub 3/H/sub 2/ in the presence of ultraviolet radiation at -60/sup 0/ to -17/sup 0/C to form a hydridoalkyl complex CpRhPMe/sub 3/RH; (b) reacting said hydridoalkyl complex with a haloform CHX/sub 3/ at -60/sup 0/ to -17/sup 0/C to form the corresponding haloalkyl complex of step (a) CpRhPMe/sub 3/RX; and (c) reacting said haloalkyl complex with halogen -60 to 25/sup 0/C to form a functional haloalkyl compound.
ET4169 Radar theory and systems
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
Challenge the future Delft University of Technology 1 Radar remote sensing of rainfall Herman Russchenberg Doppler radar signal theory and spectral estimation 2 Titel van de presentatie 2 December 2013 ET4169 - Microwaves, Radar and Remote Sensing A bit about observations 3 Titel van de presentatie 3 December 2013 ET4169 - Microwaves, Radar and Remote Sensing How to describe an apple just by looking at it? An apple is round and is green and/or red 4 Titel van de presentatie 4 December 2013
A new quasidilaton theory of massive gravity
Mukohyama, Shinji
2014-12-01
We present a new quasidilaton theory of Poincare invariant massive gravity, based on the recently proposed framework of matter coupling that makes it possible for the kinetic energy of the quasidilaton scalar to couple to both physical and fiducial metrics simultaneously. We find a scaling-type exact solution that expresses a self-accelerating de Sitter universe, and then analyze linear perturbations around it. It is shown that in a range of parameters all physical degrees of freedom have non-vanishing quadratic kinetic terms and are stable in the subhorizon limit, while the effective Newton's constant for the background is kept positive.
Theory of unidirectional spin heat conveyer
Adachi, Hiroto Maekawa, Sadamichi
2015-05-07
We theoretically investigate the unidirectional spin heat conveyer effect recently reported in the literature that emerges from the Damon-Eshbach spin wave on the surface of a magnetic material. We develop a simple phenomenological theory for heat transfer dynamics in a coupled system of phonons and the Damon-Eshbach spin wave, and demonstrate that there arises a direction-selective heat flow as a result of the competition between an isotropic heat diffusion by phonons and a unidirectional heat drift by the spin wave. The phenomenological approach can account for the asymmetric local temperature distribution observed in the experiment.
Extracting the Eliashberg Function
Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)
Extracting the Eliashberg Function Print A multitude of important chemical, physical, and biological phenomena are driven by violations of the Born-Oppenheimer approximation (BOA), which decouples electronic from nuclear motion in quantum calculations of solids. Recent advances in experimental techniques combined with ever-growing theoretical capabilities now hold the promise of presenting an unprecedented picture of these violations. By means of high-resolution angle-resolved photoemission at