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Sample records for functional theory dft

  1. Density Functional Theory (DFT) Rob Parrish

    E-Print Network [OSTI]

    Sherrill, David

    · References 2 #12;Wavefunction Approach 3 Hydrogen 421 Wavefunction at Density Isosurface. Really hard to find Easy to do this Why? Because of Hermitian Operators: Kinetic Energy Density: #12;Density Functional Approach 4 Hydrogen 421 Density (Why is it grayscale?) A bit less obvious Probably easier to find

  2. Ions in solution: Density corrected density functional theory (DC-DFT)

    SciTech Connect (OSTI)

    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.

  3. Assessing the density functional theory-based multireference configuration interaction (DFT/MRCI) method for transition metal complexes

    SciTech Connect (OSTI)

    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.

  4. How Does Ammonium Interact with Aromatic Groups? A Density Functional Theory (DFT/B3LYP) Investigation

    E-Print Network [OSTI]

    Sussman, Joel L.

    %) of the total binding energy, while the NH4 + -aromatic hydrogen bond interaction has the largest electrostaticHow Does Ammonium Interact with Aromatic Groups? A Density Functional Theory (DFT/B3LYP heterocyclic-NH3 hydrogen bond complexes, and heterocyclic-NH4 + hydrogen bond complexes. For NH4 + - complexes

  5. Introducing constricted variational density functional theory in its relaxed self-consistent formulation (RSCF-CV-DFT) as an alternative to adiabatic time dependent density functional theory for studies of charge transfer transitions

    SciTech Connect (OSTI)

    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.

  6. Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields

    E-Print Network [OSTI]

    Kevin Leung; Susan B. Rempe; Peter A. Schultz; Eduardo M. Sproviero; Victor S. Batista; Michael E. Chandross; Craig J. Medforth

    2006-10-26

    We apply Density Functional Theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an eV. The DFT+U technique, parameterized to B3LYP predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP, and ~ 0.1 Angstrom, changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first row transition metal ion complexes in a condensed-matter setting.

  7. Density-functional approaches to non-bonding interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals

    SciTech Connect (OSTI)

    Burns, Lori A [ORNL; Sherrill, David [Georgia Institute of Technology; Vazquez-Mayagoitia, Alvaro [ORNL; Sumpter, Bobby G [ORNL

    2011-01-01

    A systematic study of techniques for treating non-covalent interactions within the computationally efficient density functional theory (DFT) framework is presented through comparison to benchmark-quality evaluations of binding strength com- piled for molecular complexes of diverse size and nature. In particular, the effi- cacy of functionals deliberately crafted to encompass long-range forces, a posteri- ori DFT+dispersion corrections (DFT-D2 and DFT-D3), and exchange-hole dipole moment (XDM) theory is assessed against a large collection (469 energy points) of reference interaction energies at the CCSD(T) level of theory extrapolated to the estimated complete basis set limit. The established S22 and JSCH test sets of minimum-energy structures, as well as collections of dispersion-bound (NBC10) and hydrogen-bonded (HBC6) dissociation curves and a pairwise decomposition of a protein-ligand reaction site (HSG), comprise the chemical systems for this work. From evaluations of accuracy, consistency, and efficiency for PBE-D, BP86-D, B97-D, PBE0-D, B3LYP-D, B970-D, M05-2X, M06-2X, B97X-D, B2PLYP-D, XYG3, and B3LYP-XDM methodologies, it is concluded that distinct, often contrasting, groups of these elicit the best performance within the accessible double- or robust triple- basis set regimes and among hydrogen-bonded or dispersion-dominated complexes. For overall results, M05-2X, B97-D3, and B970-D2 yield superior values in conjunc- tion with aug-cc-pVDZ, for a mean absolute deviation of 0.41 0.49 kcal/mol, and B3LYP-D3, B97-D3, B97X-D, and B2PLYP-D3 dominate with aug-cc-pVTZ, af- fording, together with XYG3/6-311+G(3df,2p), a mean absolute deviation of 0.33 0.38 kcal/mol.

  8. Scaling Dynamical Correlation Energy from Density Functional Theory Correlation Functionals

    E-Print Network [OSTI]

    Ramachandran, Bala (Ramu)

    Scaling Dynamical Correlation Energy from Density Functional Theory Correlation Functionals B for molecules by scaling the electron correlation energy calculated by density functional theory (DFT)1 ReceiVed: February 2, 2005; In Final Form: April 18, 2005 The scaling of dynamical correlation energy

  9. The Materials genome : rapid materials screening for renewable energy using high-throughput density functional theory

    E-Print Network [OSTI]

    Jain, Anubhav, Ph.D. Massachusetts Institute of Technology

    2011-01-01

    This thesis relates to the emerging field of high-throughput density functional theory (DFT) computation for materials design and optimization. Although highthroughput DFT is a promising new method for materials discovery, ...

  10. Charge transport, configuration interaction and Rydberg states under density functional theory

    E-Print Network [OSTI]

    Cheng, Chiao-Lun

    2008-01-01

    Density functional theory (DFT) is a computationally efficient formalism for studying electronic structure and dynamics. In this work, we develop DFT-based excited-state methods to study electron transport, Rydberg excited ...

  11. Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo

    SciTech Connect (OSTI)

    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.

  12. Theoretical study of the ammonia nitridation rate on an Fe (100) surface: A combined density functional theory and kinetic Monte Carlo study

    E-Print Network [OSTI]

    Yeo, Sang Chul

    Ammonia (NH[subscript 3]) nitridation on an Fe surface was studied by combining density functional theory (DFT) and kinetic Monte Carlo (kMC) calculations. A DFT calculation was performed to obtain the energy barriers ...

  13. Hybrid DFT Functional-Based Static and Molecular Dynamics Studies of Excess Electron in Liquid Ethylene Carbonate

    SciTech Connect (OSTI)

    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 = 1–6, 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 carbon–oxygen covalent bond compared to EC-. In ab initio molecular dynamics (AIMD) simulations of EC- solvated in liquid EC, large fluctuations in the carbonyl carbon–oxygen 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.

  14. Periodic subsystem density-functional theory

    SciTech Connect (OSTI)

    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.

  15. Progress at the interface of wave-function and density-functional theories

    SciTech Connect (OSTI)

    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.

  16. 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

  17. Communication: Embedded fragment stochastic density functional theory Daniel Neuhauser, Roi Baer, and Eran Rabani

    E-Print Network [OSTI]

    Rabani, Eran

    Communication: Embedded fragment stochastic density functional theory Daniel Neuhauser, Roi Baer (2014) Communication: Embedded fragment stochastic density functional theory Daniel Neuhauser,1,a) Roi­18 Recently, we formulated KS-DFT as a statistical theory in which the electron density is determined from

  18. Integrating Experiment and Theory in Electrochemical Surface Science: Studies on the Molecular Adsorption on Noble-Metal Electrode Surfaces by Density Functional Theory, Electron Spectroscopy, and Electrochemistry 

    E-Print Network [OSTI]

    Javier, Alnald Caintic

    2013-08-05

    Computational techniques based on density functional theory (DFT) and experimental methods based on electrochemistry (EC), electrochemical scanning tunneling microscopy (EC-STM), and high-resolution electron energy loss spectroscopy (HREELS) were...

  19. Controlling the Electronic Properties of Nanodiamonds Via Surface Chemical Functionalization: A DFT Study

    E-Print Network [OSTI]

    Brown, Noam

    2013-01-01

    The electronic properties of chemically functionalized nanodiamonds are studied using density functional theory calculations. HOMO-LUMO gap and relative stabilities are calculated for different surface functionalization schemes and diamond nanocrystal morphologies. The effects of chemical decoration on the size and nature of the HOMO-LUMO gap of the various systems considered are discussed in detail. We conclude that surface chemical functionalization has the potential to become an accessible route for controlling the electronic properties of nanodiamonds.

  20. Density functional theory based generalized effective fragment potential method

    SciTech Connect (OSTI)

    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.

  1. Propagation of uncertainties in the nuclear DFT models

    E-Print Network [OSTI]

    Markus Kortelainen

    2014-09-04

    Parameters of the nuclear density functional theory (DFT) models are usually adjusted to experimental data. As a result they carry certain theoretical error, which, as a consequence, carries out to the predicted quantities. In this work we address the propagation of theoretical error, within the nuclear DFT models, from the model parameters to the predicted observables. In particularly, the focus is set on the Skyrme energy density functional models.

  2. A density functional theory study of the correlation between analyte basicity, ZnPc adsorption strength, and sensor response

    E-Print Network [OSTI]

    Kummel, Andrew C.

    A density functional theory study of the correlation between analyte basicity, ZnPc adsorption Received 4 January 2009; accepted 27 April 2009; published online 28 May 2009 Density functional theory DFT of their electron donating ability or Lewis basicity. With the exception of the most basic analyte investigated

  3. Accuracy of density functional theory in predicting formation energies of ternary oxides from binary oxides and its implication on phase stability

    E-Print Network [OSTI]

    Hautier, Geoffroy

    The evaluation of reaction energies between solids using density functional theory (DFT) is of practical importance in many technological fields and paramount in the study of the phase stability of known and predicted ...

  4. Intrinsic point-defect equilibria in tetragonal ZrO[subscript 2]: Density functional theory analysis with finite-temperature effects

    E-Print Network [OSTI]

    Youssef, Mostafa Youssef Mahm

    We present a density functional theory (DFT) framework taking into account the finite temperature effects to quantitatively understand and predict charged defect equilibria in a metal oxide. Demonstration of this approach ...

  5. Role of exchange in density-functional theory for weakly interacting systems: Quantum Monte Carlo analysis of electron density and interaction energy

    E-Print Network [OSTI]

    Grossman, Jeffrey C.

    We analyze the density-functional theory (DFT) description of weak interactions by employing diffusion and reptation quantum Monte Carlo (QMC) calculations, for a set of benzene-molecule complexes. While the binding energies ...

  6. Density Functional Theory investigations of titanium gamma-surfaces and stacking faults

    E-Print Network [OSTI]

    Benoit, Magali; Morillo, Joseph

    2015-01-01

    Properties of hcp-Ti such as elastic constants, stacking faults and gamma-surfaces are computed using Density Functional Theory (DFT) and two central force Embedded Atom interaction Models (EAM). The results are compared to previously published calculations and to predicting models. Their implications on the plastic properties of hcp-Ti are discussed.

  7. Spin densities from subsystem density-functional theory: Assessment and application to a photosynthetic reaction center complex model

    SciTech Connect (OSTI)

    Solovyeva, Alisa [Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Technical University Braunschweig, Institute for Physical and Theoretical Chemistry, Hans-Sommer-Str. 10, 38106 Braunschweig (Germany); Pavanello, Michele [Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden (Netherlands); Neugebauer, Johannes [Technical University Braunschweig, Institute for Physical and Theoretical Chemistry, Hans-Sommer-Str. 10, 38106 Braunschweig (Germany)

    2012-05-21

    Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a {pi}-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations. In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.

  8. Pressure Correction in Classical Density Functional Theory: Hyper Netted Chain and Hard Sphere Bridge Functionals

    E-Print Network [OSTI]

    Volodymyr Sergiievskyi; Guillaume Jeanmairet; Maximilien Levesque; Daniel Borgis

    2015-09-04

    Low accuracy of the Solvation Free Energy (SFE) calculation is a known problem of the numerical methods of the Integral Equation Theory of Liquids and the Classical Density Functional Theory (Classical DFT). Although functionals with empirical corrections can essentially improve the predictability of the methods, their universality is still a question. In our recent paper we connected the SFE calculation errors with the incorrect pressure in the Classical DFT and proposed the a posteriory correction to improve the results (J. Phys. Chem. Lett., 5, 1925-1942 ). This paper raised a discussion in the community. In particular, recently appeared a critical reply where pointed some thermodynamical inconsistencies of the derivations in our paper (J. Chem. Theory Comput., 11, 378-380). In the present work we re-derive the pressure correction in a more simple way and show that despite the inaccuracies during the derivation, the final form of the previously derived correction is correct. We also test the applicability of the proposed correction to the functionals which include a three- and many- body terms from the fundamental measure theory (FMT) for hard sphere fluid. We test all the functionals on a set of model systems and discuss the obtained results.

  9. Quantification of Uncertainties in Nuclear Density Functional theory

    E-Print Network [OSTI]

    N. Schunck; J. D. McDonnell; D. Higdon; J. Sarich; S. Wild

    2014-09-17

    Reliable predictions of nuclear properties are needed as much to answer fundamental science questions as in applications such as reactor physics or data evaluation. Nuclear density functional theory is currently the only microscopic, global approach to nuclear structure that is applicable throughout the nuclear chart. In the past few years, a lot of effort has been devoted to setting up a general methodology to assess theoretical uncertainties in nuclear DFT calculations. In this paper, we summarize some of the recent progress in this direction. Most of the new material discussed here will be be published in separate articles.

  10. Tuning Range-Separated Density Functional Theory for Photocatalytic Water Splitting Systems

    E-Print Network [OSTI]

    Bokareva, Olga S; Bokarev, Sergey I; Kühn, Oliver

    2015-01-01

    We discuss the applicability of long-range separated density functional theory (DFT) to the prediction of electronic transitions of a particular photocatalytic system based on an Ir(III) photosensitizer (IrPS). Special attention is paid to the charge-transfer properties which are of key importance for the photoexcitation dynamics, but and cannot be correctly described by means of conventional DFT. The optimization of the range-separation parameter is discussed for IrPS including its complexes with electron donors and acceptors used in photocatalysis. Particular attention is paid to the problems arising for a description of medium effects by a polarizable continuum model.

  11. Time Dependent Density Functional Theory An introduction

    E-Print Network [OSTI]

    Botti, Silvana

    Time Dependent Density Functional Theory An introduction Francesco Sottile LSI, Ecole Polytechnique (ETSF) Time Dependent Density Functional Theory Palaiseau, 7 February 2012 1 / 32 #12;Outline 1 Frontiers 4 Perspectives and Resources Francesco Sottile (ETSF) Time Dependent Density Functional Theory

  12. Density functional theory study on the interstitial chemical shifts of main-group-element centered hexazirconium halide clusters; synthetic control of speciation in [(Zr6ZCl12)] (Z = B, C)-based mixed ligand complexes 

    E-Print Network [OSTI]

    Shen, Jingyi

    2005-08-29

    The correlation between NMR chemical shifts of interstitial atoms and electronic structures of boron- and carbon-centered hexazirconium halide clusters was investigated by density functional theory (DFT) calculation. The ...

  13. ATLAS: A Real-Space Finite-Difference Implementation of Orbital-Free Density Functional Theory

    E-Print Network [OSTI]

    Wenhui Mi; Xuecheng Shao; Chuanxun Su; Yuanyuan Zhou; Shoutao Zhang; Quan Li; Hui Wang; Lijun Zhang; Maosheng Miao; Yanchao Wang; Yanming Ma

    2015-07-28

    Orbital-free density functional theory (OF-DFT) is a promising method for large-scale quantum mechanics simulation as it provides a good balance of accuracy and computational cost. Its applicability to large-scale simulations has been aided by progress in constructing kinetic energy functionals and local pseudopotentials. However, the widespread adoption of OF-DFT requires further improvement in its efficiency and robustly implemented software. Here we develop a real-space finite-difference method for the numerical solution of OF-DFT in periodic systems. Instead of the traditional self-consistent method, a powerful scheme for energy minimization is introduced to solve the Euler--Lagrange equation. Our approach engages both the real-space finite-difference method and a direct energy-minimization scheme for the OF-DFT calculations. The method is coded into the ATLAS software package and benchmarked using periodic systems of solid Mg, Al, and Al$_{3}$Mg. The test results show that our implementation can achieve high accuracy, efficiency, and numerical stability for large-scale simulations.

  14. ATLAS: A Real-Space Finite-Difference Implementation of Orbital-Free Density Functional Theory

    E-Print Network [OSTI]

    Mi, Wenhui; Sua, Chuanxun; Zhoua, Yuanyuan; Zhanga, Shoutao; Lia, Quan; Wanga, Hui; Zhang, Lijun; Miao, Maosheng; Wanga, Yanchao; Ma, Yanming

    2015-01-01

    Orbital-free density functional theory (OF-DFT) is a promising method for large-scale quantum mechanics simulation as it provides a good balance of accuracy and computational cost. Its applicability to large-scale simulations has been aided by progress in constructing kinetic energy functionals and local pseudopotentials. However, the widespread adoption of OF-DFT requires further improvement in its efficiency and robustly implemented software. Here we develop a real-space finite-difference method for the numerical solution of OF-DFT in periodic systems. Instead of the traditional self-consistent method, a powerful scheme for energy minimization is introduced to solve the Euler--Lagrange equation. Our approach engages both the real-space finite-difference method and a direct energy-minimization scheme for the OF-DFT calculations. The method is coded into the ATLAS software package and benchmarked using periodic systems of solid Mg, Al, and Al$_{3}$Mg. The test results show that our implementation can achieve ...

  15. A Systematic Study of Chloride Ion Solvation in Water using van der Waals Inclusive Hybrid Density Functional Theory

    E-Print Network [OSTI]

    Bankura, Arindam; DiStasio, Robert A; Swartz, Charles W; Klein, Michael L; Wu, Xifan

    2015-01-01

    In this work, the solvation and electronic structure of the aqueous chloride ion solution was investigated using Density Functional Theory (DFT) based \\textit{ab initio} molecular dynamics (AIMD). From an analysis of radial distribution functions, coordination numbers, and solvation structures, we found that exact exchange ($E_{\\rm xx}$) and non-local van der Waals (vdW) interactions effectively \\textit{weaken} the interactions between the Cl$^-$ ion and the first solvation shell. With a Cl-O coordination number in excellent agreement with experiment, we found that most configurations generated with vdW-inclusive hybrid DFT exhibit 6-fold coordinated distorted trigonal prism structures, which is indicative of a significantly disordered first solvation shell. By performing a series of band structure calculations on configurations generated from AIMD simulations with varying DFT potentials, we found that the solvated ion orbital energy levels (unlike the band structure of liquid water) strongly depend on the un...

  16. Temperature Dependent Magnon-Phonon Coupling in bcc Fe from Theory and Experiment

    E-Print Network [OSTI]

    Tai, Yu-Chong

    - actions in bcc Fe. Parameter-free electronic structure calculations like den- sity functional theory (DFT moments (DLM) molecular dynamics [1], magnetic empirical poten- tials [2

  17. Density functional theory study of transition metal porphine adsorption on gold surface and electric field induced conformation changes.

    SciTech Connect (OSTI)

    Batista, Victor S. (Yale University, New Haven, CT); Chandross, Michael Evan; Leung, Kevin; Sporviero, Eduardo (Yale University, New Haven, CT); Schultz, Peter Andrew; Rempe, Susan B.

    2005-06-01

    We apply density functional theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew?Burke?Ernzerhof exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an electronvolt. The DFT+U technique, parametrized to B3LYP-predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than that of PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP and 0.1 {angstrom} changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first-row transition metal ion complexes in a condensed-matter setting.

  18. Wide range equation of state for fluid hydrogen from density functional theory

    SciTech Connect (OSTI)

    Wang, Cong; Zhang, Ping [Institute of Applied Physics and Computational Mathematics, P.O. Box 8009, Beijing 100088 (China) [Institute of Applied Physics and Computational Mathematics, P.O. Box 8009, Beijing 100088 (China); Center for Applied Physics and Technology, Peking University, Beijing 100871 (China)

    2013-09-15

    Wide range equation of state (EOS) for liquid hydrogen is ultimately obtained by combining two kinds of density functional theory (DFT) molecular dynamics simulations, namely, first-principles molecular dynamics simulations and orbital-free molecular dynamics simulations. Specially, the present introduction of short cutoff radius pseudopotentials enables the EOS to be available in the range from 9.82 × 10{sup ?4} to 1.347 × 10{sup 3} g/cm{sup 3} and up to 5 × 10{sup 7} K. By comprehensively comparing with various attainable experimental and theoretical data, we derive the conclusion that our DFT-EOS can be readily and reliably applied to hydrodynamic simulations of the inertial confinement fusion.

  19. Combinatorial density functional theory-based screening of surface alloys for the oxygen reduction reaction.

    SciTech Connect (OSTI)

    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.

  20. Jacek Dobaczewski Density functional theory and energy

    E-Print Network [OSTI]

    Dobaczewski, Jacek

    Jacek Dobaczewski Density functional theory and energy density functionals in nuclear physics Jacek UNEDFCollaboration,http://unedf.org/ Universal Nuclear Energy Density FunctionalUniversal Nuclear Energy Density in Poland per voivodship Energy density functional 245 647 Price voivodship functional 654 763 295 580

  1. Uncertainty Quantification for Nuclear Density Functional Theory...

    Office of Scientific and Technical Information (OSTI)

    Uncertainty Quantification for Nuclear Density Functional Theory and Information Content of New Measurements Citation Details In-Document Search Title: Uncertainty Quantification...

  2. Uncertainty Quantification for Nuclear Density Functional Theory...

    Office of Scientific and Technical Information (OSTI)

    Uncertainty Quantification for Nuclear Density Functional Theory and Information Content of New Measurements Citation Details In-Document Search This content will become publicly...

  3. Zinc surface complexes on birnessite: A density functional theory study

    SciTech Connect (OSTI)

    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.

  4. A Systematic Study of Chloride Ion Solvation in Water using van der Waals Inclusive Hybrid Density Functional Theory

    E-Print Network [OSTI]

    Arindam Bankura; Biswajit Santra; Robert A. DiStasio Jr.; Charles W. Swartz; Michael L. Klein; Xifan Wu

    2015-03-25

    In this work, the solvation and electronic structure of the aqueous chloride ion solution was investigated using Density Functional Theory (DFT) based \\textit{ab initio} molecular dynamics (AIMD). From an analysis of radial distribution functions, coordination numbers, and solvation structures, we found that exact exchange ($E_{\\rm xx}$) and non-local van der Waals (vdW) interactions effectively \\textit{weaken} the interactions between the Cl$^-$ ion and the first solvation shell. With a Cl-O coordination number in excellent agreement with experiment, we found that most configurations generated with vdW-inclusive hybrid DFT exhibit 6-fold coordinated distorted trigonal prism structures, which is indicative of a significantly disordered first solvation shell. By performing a series of band structure calculations on configurations generated from AIMD simulations with varying DFT potentials, we found that the solvated ion orbital energy levels (unlike the band structure of liquid water) strongly depend on the underlying molecular structures. In addition, these orbital energy levels were also significantly affected by the DFT functional employed for the electronic structure; as the fraction of $E_{\\rm xx}$ was increased, the gap between the highest occupied molecular orbital of Cl$^-$ and the valence band maximum of liquid water steadily increased towards the experimental value.

  5. Time Dependent Density Functional Theory An Introduction

    E-Print Network [OSTI]

    Botti, Silvana

    Time Dependent Density Functional Theory An Introduction Francesco Sottile Laboratoire des Solides) Belfast, 29 Jun 2007 Time Dependent Density Functional Theory Francesco Sottile #12;Intro Formalism Linear Response Formalism 3 TDDFT in practice: The ALDA: Achievements and Shortcomings 4 Resources Time

  6. Electronic and optical properties of pure and modified diamondoids studied by many-body perturbation theory and time-dependent density functional theory

    SciTech Connect (OSTI)

    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.

  7. Semiclassical Origins of Density Functionals Peter Elliott, Donghyung Lee, Attila Cangi, and Kieron Burke

    E-Print Network [OSTI]

    Burke, Kieron

    Semiclassical Origins of Density Functionals Peter Elliott, Donghyung Lee, Attila Cangi, and Kieron world of pure density functional theory (DFT), i.e., Thomas-Fermi (TF) and related theories

  8. Validating density-functional theory simulations at high energy-density conditions with liquid krypton shock experiments to 850 GPa on Sandia's Z machine

    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

  9. Validating density-functional theory simulations at high energy-density conditions with liquid krypton shock experiments to 850 GPa on Sandia's Z machine

    SciTech Connect (OSTI)

    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.

  10. On the Accuracy of van der Waals Inclusive Density-Functional Theory Exchange-Correlation Functionals for Ice at Ambient and High Pressures

    E-Print Network [OSTI]

    Biswajit Santra; Ji?í Klimeš; Alexandre Tkatchenko; Dario Alfè; Ben Slater; Angelos Michaelides; Roberto Car; Matthias Scheffler

    2014-08-14

    Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive properties of the various phases, causing certain phases to be absent from the phase diagram. Therefore, room for improvement in the description of water at ambient and high pressures remains and we suggest that because of the stern test the high pressure ice phases pose they should be used in future benchmark studies of simulation methods for water.

  11. On the Accuracy of van der Waals Inclusive Density-Functional Theory Exchange-Correlation Functionals for Ice at Ambient and High Pressures

    E-Print Network [OSTI]

    Santra, Biswajit; Tkatchenko, Alexandre; Alfè, Dario; Slater, Ben; Michaelides, Angelos; Car, Roberto; Scheffler, Matthias

    2013-01-01

    Density-functional theory (DFT) has been widely used to study water and ice for at least 20 years. However, the reliability of different DFT exchange-correlation (xc) functionals for water remains a matter of considerable debate. This is particularly true in light of the recent development of DFT based methods that account for van der Waals (vdW) dispersion forces. Here, we report a detailed study with several xc functionals (semi-local, hybrid, and vdW inclusive approaches) on ice Ih and six proton ordered phases of ice. Consistent with our previous study [Phys. Rev. Lett. 107, 185701 (2011)] which showed that vdW forces become increasingly important at high pressures, we find here that all vdW inclusive methods considered improve the relative energies and transition pressures of the high-pressure ice phases compared to those obtained with semi-local or hybrid xc functionals. However, we also find that significant discrepancies between experiment and the vdW inclusive approaches remain in the cohesive proper...

  12. Hexakis(4-phormylphenoxy)cyclotriphosphazene: X-ray and DFT-calculated structures

    SciTech Connect (OSTI)

    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.

  13. About density functional theory interpretation

    E-Print Network [OSTI]

    Kirill Koshelev

    2015-05-28

    Two forms of relativistic density functional are derived from Dirac equation. Based on their structure analysis model of split electron is proposed. In this model electric charge and mass of electron behave like two point-like particles. It is shown that two electrons obeying this model cannot occupy the same quantum state. Empirical verification of the model is discussed.

  14. Magnetic fields and density functional theory

    SciTech Connect (OSTI)

    Salsbury Jr., Freddie

    1999-02-01

    A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules.

  15. Density Functional Theory Calculations of Mass Transport in UO2

    SciTech Connect (OSTI)

    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.

  16. Error Analysis in Nuclear Density Functional Theory (Journal...

    Office of Scientific and Technical Information (OSTI)

    Error Analysis in Nuclear Density Functional Theory Citation Details In-Document Search Title: Error Analysis in Nuclear Density Functional Theory Authors: Schunck, N ; McDonnell,...

  17. Error Analysis in Nuclear Density Functional Theory (Journal...

    Office of Scientific and Technical Information (OSTI)

    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...

  18. Anchoring Pd nanoclusters onto pristine and functionalized single-wall carbon nanotubes: A combined DFT and experimental study

    E-Print Network [OSTI]

    Resasco, Daniel

    in heteroge- neous catalysis [1], fuel cells [2,3] and sensors [4­6]. Both multi- and single-wall carbon- nation on the organic phase. This combination is particularly relevant in the upgrading of bio) or oxygen-functionalized [15]. The functional groups were introduced by treating the SWCNT with HNO3 3 M

  19. Density functional theory for carbon dioxide crystal

    SciTech Connect (OSTI)

    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.

  20. Fusion using time-dependent density-constrained DFT

    E-Print Network [OSTI]

    R. Keser; A. S. Umar; V. E. Oberacker; J. A. Maruhn; P. -G. Reinhard

    2014-02-06

    We present results for calculating fusion cross-sections using a new microscopic approach based on a time-dependent density-constrained DFT calculations. The theory is implemented by using densities and other information obtained from TDDFT time-evolution of the nuclear system as constraint on the density for DFT calculations.

  1. Density functional theory study of (OCS)2^-

    E-Print Network [OSTI]

    Bilalbegovic, G

    2007-01-01

    The structural and electronic properties of the carbonyl sulfide dimer anion are calculated using density functional theory within a pseudopotential method. Three geometries are optimized and investigated: C2v and C2 symmetric, as well as one asymmetric structure. A distribution of an excess charge in three isomers are studied by the Hirshfeld method. In an asymmetric (OCS)2^- isomer the charge is not equally divided between the two moieties, but it is distributed as OCS^{-0.6} OCS^{-0.4}. Low-lying excitation levels of three isomers are compared using the time-dependent density functional theory in the Casida approach.

  2. Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)

    SciTech Connect (OSTI)

    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.

  3. Adsorption of silver dimer on graphene - A DFT study

    SciTech Connect (OSTI)

    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.

  4. On the cosmological mass function theory

    E-Print Network [OSTI]

    A. Del Popolo

    2006-09-06

    This paper provides, from one side, a review of the theory of the cosmological mass function from a theoretical point of view, starting from the seminal paper of Press & Shechter (1974) to the last developments (Del Popolo & Gambera (1998, 1999), Sheth & Tormen 1999 (ST), Sheth, Mo & Tormen 2001 (ST1), Jenkins et al. 2001 (J01), Shet & Tormen 2002 (ST2), Del Popolo 2002a, Yagi et al. 2004 (YNY)), and from another side some improvements on the multiplicity function models in literature. ...

  5. Density Functional Theory Models for Radiation Damage

    E-Print Network [OSTI]

    Density Functional Theory Models for Radiation Damage S.L. Dudarev EURATOM/CCFE Fusion Association and informative as the most advanced experimental techniques developed for the observation of radiation damage investigation and assessment of radiation damage effects, offering new insight into the origin of temperature

  6. Thermally-assisted-occupation density functional theory with generalized-gradient approximations

    SciTech Connect (OSTI)

    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.

  7. VOLUME 79, NUMBER 20 P H Y S I C A L R E V I E W L E T T E R S 17 NOVEMBER 1997 Sparsity of the Density Matrix in Kohn-Sham Density Functional Theory

    E-Print Network [OSTI]

    Baer, Roi

    energy and Car-Parrinello approaches [1,2]. These methods are, however, capable of dealing with a limited functional theory (DFT) of the many-electron ground state energy has served as a basis for numerous large to contribute to these efforts by introducing a new analytical method to derive estimates for the range

  8. Including screening in van der Waals corrected density functional theory calculations: The case of atoms and small molecules physisorbed on graphene

    SciTech Connect (OSTI)

    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.

  9. MiniDFT

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity ofkandz-cm11 Outreach Home Room NewsInformationJessework uses concrete7 Assessment ofLana7,MimickingTheMiniDFT MiniDFT

  10. MiniDFT

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity ofkandz-cm11 Outreach Home Room NewsInformationJessework uses concrete7 Assessment ofLana7,MimickingTheMiniDFT MiniDFTMiniDFT

  11. Higher-order adaptive finite-element methods for Kohn–Sham density functional theory

    SciTech Connect (OSTI)

    Motamarri, P. [Department of Mechanical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States)] [Department of Mechanical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Nowak, M.R. [Department of Electrical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States)] [Department of Electrical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States); Leiter, K.; Knap, J. [U.S. Army Research Labs, Aberdeen Proving Ground, Aberdeen, MD 21001 (United States)] [U.S. Army Research Labs, Aberdeen Proving Ground, Aberdeen, MD 21001 (United States); Gavini, V., E-mail: vikramg@umich.edu [Department of Mechanical Engineering, University of Michigan, Ann Arbor, MI 48109 (United States)

    2013-11-15

    We present an efficient computational approach to perform real-space electronic structure calculations using an adaptive higher-order finite-element discretization of Kohn–Sham density-functional theory (DFT). To this end, we develop an a priori mesh-adaption technique to construct a close to optimal finite-element discretization of the problem. We further propose an efficient solution strategy for solving the discrete eigenvalue problem by using spectral finite-elements in conjunction with Gauss–Lobatto quadrature, and a Chebyshev acceleration technique for computing the occupied eigenspace. The proposed approach has been observed to provide a staggering 100–200-fold computational advantage over the solution of a generalized eigenvalue problem. Using the proposed solution procedure, we investigate the computational efficiency afforded by higher-order finite-element discretizations of the Kohn–Sham DFT problem. Our studies suggest that staggering computational savings—of the order of 1000-fold—relative to linear finite-elements can be realized, for both all-electron and local pseudopotential calculations, by using higher-order finite-element discretizations. On all the benchmark systems studied, we observe diminishing returns in computational savings beyond the sixth-order for accuracies commensurate with chemical accuracy, suggesting that the hexic spectral-element may be an optimal choice for the finite-element discretization of the Kohn–Sham DFT problem. A comparative study of the computational efficiency of the proposed higher-order finite-element discretizations suggests that the performance of finite-element basis is competing with the plane-wave discretization for non-periodic local pseudopotential calculations, and compares to the Gaussian basis for all-electron calculations to within an order of magnitude. Further, we demonstrate the capability of the proposed approach to compute the electronic structure of a metallic system containing 1688 atoms using modest computational resources, and good scalability of the present implementation up to 192 processors.

  12. Nuclear fission in covariant density functional theory

    E-Print Network [OSTI]

    A. V. Afanasjev; H. Abusara; P. Ring

    2013-09-12

    The current status of the application of covariant density functional theory to microscopic description of nuclear fission with main emphasis on superheavy nuclei (SHN) is reviewed. The softness of SHN in the triaxial plane leads to an emergence of several competing fission pathes in the region of the inner fission barrier in some of these nuclei. The outer fission barriers of SHN are considerably affected both by triaxiality and octupole deformation.

  13. 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

  14. Mixing of equations of state for xenon-deuterium using density functional theory

    SciTech Connect (OSTI)

    Magyar, Rudolph J.; Mattsson, Thomas R. [Sandia National Laboratories, Albuquerque, New Mexico 87185 (United States)

    2013-03-15

    We report on a theoretical study of equation of state (EOS) properties of fluid and dense plasma mixtures of xenon and deuterium to explore and illustrate the basic physics of the mixing of a light element with a heavy element. Accurate EOS models are crucial to achieve high-fidelity hydrodynamics simulations of many high-energy-density phenomena, for example inertial confinement fusion and strong shock waves. While the EOS is often tabulated for separate species, the equation of state for arbitrary mixtures is generally not available, requiring properties of the mixture to be approximated by combining physical properties of the pure systems. Density functional theory (DFT) at elevated-temperature is used to assess the thermodynamics of the xenon-deuterium mixture at different mass ratios. The DFT simulations are unbiased as to elemental species and therefore provide comparable accuracy when describing total energies, pressures, and other physical properties of mixtures as they do for pure systems. The study focuses on addressing the accuracy of different mixing rules in the temperature range 1000-40 000 K for pressures between 100 and 600 GPa (1-6 Mbar), thus, including the challenging warm dense matter regime of the phase diagram. We find that a mix rule taking into account pressure equilibration between the two species performs very well over the investigated range.

  15. Density functional theory calculations of stability and diffusion mechanisms of impurity atoms in Ge crystals

    SciTech Connect (OSTI)

    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.

  16. Near Surface Stoichiometry in UO 2 : 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

    2015-01-01

    The mechanisms of oxygen stoichiometry variation in UO2at 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 UO2near 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 UO2have 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 bymore »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 UO2prefers to be hypostoichiometric, although the surface is near-stoichiometric.« less

  17. Dynamics of observables and exactly solvable quantum problems: Using time-dependent density functional theory to control quantum systems

    E-Print Network [OSTI]

    Mehdi Farzanehpour; I. V. Tokatly

    2015-06-29

    We use analytic (current) density-potential maps of time-dependent (current) density functional theory (TD(C)DFT) to inverse engineer analytically solvable time-dependent quantum problems. In this approach the driving potential (the control signal) and the corresponding solution of the Schr\\"odinger equation are parametrized analytically in terms of the basic TD(C)DFT observables. We describe the general reconstruction strategy and illustrate it with a number of explicit examples. First we consider the real space one-particle dynamics driven by a time-dependent electromagnetic field and recover, from the general TDDFT reconstruction formulas, the known exact solution for a driven oscillator with a time-dependent frequency. Then we use analytic maps of the lattice TD(C)DFT to control quantum dynamics in a discrete space. As a first example we construct a time-dependent potential which generates prescribed dynamics on a tight-binding chain. Then our method is applied to the dynamics of spin-1/2 driven by a time dependent magnetic field. We design an analytic control pulse that transfers the system from the ground to excited state and vice versa. This pulse generates the spin flip thus operating as a quantum NOT gate.

  18. Subsystem Density-Functional Theory as an Effective Tool for Modeling Ground and Excited States, their Dynamics, and Many-Body Interactions

    E-Print Network [OSTI]

    Krishtal, Alisa; Genova, Alessandro; Pavanello, Michele

    2015-01-01

    Subsystem Density-Functional Theory (DFT) is an emerging technique for calculating the electronic structure of complex molecular and condensed phase systems. In this topical review, we focus on some recent advances in this field related to the computation of condensed phase systems, their excited states, and the evaluation of many-body interactions between the subsystems. As subsystem DFT is in principle an exact theory, any advance in this field can have a dual role. One is the possible applicability of a resulting method in practical calculations. The other is the possibility of shedding light on some quantum-mechanical phenomenon which is more easily treated by subdividing a supersystem into subsystems. An example of the latter is many-body interactions. In the discussion, we present some recent work from our research group as well as some new results, casting them in the current state-of-the-art in this review as comprehensively as possible.

  19. Electronic Structure via Potential Functional Approximations Attila Cangi,1

    E-Print Network [OSTI]

    Burke, Kieron

    Elliott,2 Kieron Burke,1 and E. K. U. Gross3 1 Department of Chemistry, University of California, 1102 of density-functional theory (DFT), suggested by Thomas [1] and Fermi [2] (TF) and made formally exact

  20. Symmetry energy in nuclear density functional theory

    E-Print Network [OSTI]

    W. Nazarewicz; P. -G. Reinhard; W. Satula; D. Vretenar

    2013-07-22

    The nuclear symmetry energy represents a response to the neutron-proton asymmetry. In this survey we discuss various aspects of symmetry energy in the framework of nuclear density functional theory, considering both non-relativistic and relativistic self-consistent mean-field realizations side-by-side. Key observables pertaining to bulk nucleonic matter and finite nuclei are reviewed. Constraints on the symmetry energy and correlations between observables and symmetry-energy parameters, using statistical covariance analysis, are investigated. Perspectives for future work are outlined in the context of ongoing experimental efforts.

  1. Fitting Skyrme functionals using linear response theory

    E-Print Network [OSTI]

    A. Pastore; D. Davesne; K. Bennaceur; J. Meyer; V. Hellemans

    2012-10-30

    Recently, it has been recently shown that the linear response theory in symmetric nuclear matter can be used as a tool to detect finite size instabilities for different Skyrme functionals. In particular it has been shown that there is a correlation between the density at which instabilities occur in infinite matter and the instabilities in finite nuclei. In this article we present a new fitting protocol that uses this correlation to add new additional constraint in Symmetric Infinite Nuclear Matter in order to ensure the stability of finite nuclei against matter fluctuation in all spin and isospin channels. As an application, we give the parameters set for a new Skyrme functional which includes central and spin-orbit parts and which is free from instabilities by construction.

  2. Electronically Excited States of Vitamin B12: Benchmark Calculations Including Time-Dependent Density Functional Theory and Correlated Ab Initio Methods

    E-Print Network [OSTI]

    Kornobis, Karina; Wong, Bryan M; Lodowski, Piotr; Jaworska, Maria; Andruniów, Tadeusz; Rudd, Kenneth; Kozlowski, Pawel M; 10.1021/jp110914y

    2011-01-01

    Time-dependent density functional theory (TD-DFT) and correlated ab initio methods have been applied to the electronically excited states of vitamin B12 (cyanocobalamin or CNCbl). Different experimental techniques have been used to probe the excited states of CNCbl, revealing many issues that remain poorly understood from an electronic structure point of view. Due to its efficient scaling with size, TD-DFT emerges as one of the most practical tools that can be used to predict the electronic properties of these fairly complex molecules. However, the description of excited states is strongly dependent on the type of functional used in the calculations. In the present contribution, the choice of a proper functional for vitamin B12 was evaluated in terms of its agreement with both experimental results and correlated ab initio calculations. Three different functionals, i.e. B3LYP, BP86, and LC-BLYP, were tested. In addition, the effect of relative contributions of DFT and HF to the exchange-correlation functional ...

  3. Local pressure of confined fluids inside nanoslit pores -- A density functional theory prediction

    E-Print Network [OSTI]

    F. Heidari; G. A. Mansoori; E. Keshavarzi

    2013-07-18

    In this work, the local pressure of fluids confined inside nanoslit pores is predicted within the framework of the density functional theory. The Euler-Lagrange equation in the density functional theory of statistical mechanics is used to obtain the force balance equation which leads to a general equation to predict the local normal component of the pressure tensor. Our approach yields a general equation for predicting the normal pressure of confined fluids and it satisfies the exact bulk thermodynamics equation when the pore width approaches infinity. As two basic examples, we report the solution of the general equation for hard-sphere (HS) and Lennard-Jones (LJ) fluids confined between two parallel-structureless hard walls. To do so, we use the modified fundamental measure theory (mFMT) to obtain the normal pressure for hard-sphere confined fluid and mFMT incorporated with the Rosenfeld perturbative DFT for the LJ fluid. Effects of different variables including pore width, bulk density and temperature on the behavior of normal pressure are studied and reported. Our predicted results show that in both HS and LJ cases the confined fluids normal pressure has an oscillatory behavior and the number of oscillations increases with bulk density and temperature. The oscillations also become broad and smooth with pore width at a constant temperature and bulk density. In comparison with the HS confined fluid, the values of normal pressure for the LJ confined fluid as well as its oscillations at all distances from the walls are less profound.

  4. Orbital-optimized density cumulant functional theory

    SciTech Connect (OSTI)

    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.

  5. Density functional theory study of chemical sensing on surfaces of single-layer MoS{sub 2} and graphene

    SciTech Connect (OSTI)

    Mehmood, F.; Pachter, R., E-mail: ruth.pachter@us.af.mil [Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433 (United States)

    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.

  6. Self-interaction-free density-functional theoretical study of the electronic structure of spherical and vertical quantum dots

    E-Print Network [OSTI]

    Jiang, T. F.; Tong, Xiao-Min; Chu, Shih-I

    2001-01-09

    We study the electronic structure and shell-filling effects of both spherical and vertical quantum dots by means of the density functional theory (DFT) with optimized effective potential (OEP) and self-interaction-correction (SIC) recently developed...

  7. Quantifying the importance of orbital over spin correlations in delta-Pu within density-functional theory

    SciTech Connect (OSTI)

    Soderlind, P; Wolfer, W

    2007-07-27

    Spin and orbital and electron correlations are known to be important when treating the high-temperature {delta} phase of plutonium within the framework of density-functional theory (DFT). One of the more successful attempts to model {delta}-Pu within this approach has included condensed-matter generalizations of Hund's three rules for atoms, i.e., spin polarization, orbital polarization, and spin-orbit coupling. Here they perform a quantitative analysis of these interactions relative rank for the bonding and electronic structure in {delta}-Pu within the DFT model. The result is somewhat surprising in that spin-orbit coupling and orbital polarization are far more important than spin polarization for a realistic description of {delta}-Pu. They show that these orbital correlations on their own, without any formation of magnetic spin moments, can account for the low atomic density of the {delta} phase with a reasonable equation-of-state. In addition, this unambiguously non-magnetic (NM) treatment produces a one-electron spectra with resonances close to the Fermi level consistent with experimental valence band photoemission spectra.

  8. DENSITY FUNCTIONAL THEORY OF NORMAL AND SUPERCONDUCTING ELECTRON LIQUIDS: EXPLICIT

    E-Print Network [OSTI]

    Gross, E.K.U.

    22 5.1 Green's functions for the non-interacting system . . . . . . . . . . . . . . . 22 5 the Green's functions . . . . . . . . . . . . 28 5.5 Poles of the zero-order Green's functions theory is to describe a many-electron system exclusively and completely in terms of its ground

  9. Hybrid Dynamic Density Functional Theory for Polymer Melts and Blends

    E-Print Network [OSTI]

    Takashi Honda; Toshihiro Kawakatsu

    2006-09-05

    We propose a high-speed and accurate hybrid dynamic density functional theory for the computer simulations of the phase separation processes of polymer melts and blends. The proposed theory is a combination of the dynamic self-consistent field (SCF) theory and a time-dependent Ginzburg-Landau type theory with the random phase approximation (GRPA). The SCF theory is known to be accurate in evaluating the free energy of the polymer systems in both weak and strong segregation regions although it has a disadvantage of the requirement of a considerable amount of computational cost. On the other hand, the GRPA theory has an advantage of much smaller amount of required computational cost than the SCF theory while its applicability is limited to the weak segregation region. To make the accuracy of the SCF theory and the high-performance of the GRPA theory compatible, we adjust the chemical potential of the GRPA theory by using the SCF theory every constant time steps in the dynamic simulations. The performance of the GRPA and the hybrid theories is tested by using several systems composed of an A/B homopolymer, an AB diblock copolymer, or an ABC triblock copolymer. Using the hybrid theory, we succeeded in reproducing the metastable complex phase-separated domain structures of an ABC triblock copolymer observed by experiments.

  10. Optimal Transportation Theory with Repulsive Costs

    E-Print Network [OSTI]

    Simone Di Marino; Augusto Gerolin; Luca Nenna

    2015-06-15

    This paper intents to present the state of art and recent developments of the optimal transportation theory with many marginals for a class of repulsive cost functions. We introduce some aspects of the Density Functional Theory (DFT) from a mathematical point of view, and revisit the theory of optimal transport from its perspective. Moreover, in the last three sections, we describe some recent and new theoretical and numerical results obtained for the Coulomb cost, the repulsive harmonic cost and the determinant cost.

  11. Ensemble density variational methods with self- and ghost-interaction-corrected functionals

    SciTech Connect (OSTI)

    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.

  12. A Classical Density-Functional Theory for Describing Water Interfaces

    E-Print Network [OSTI]

    Jessica Hughes; Eric Krebs; David Roundy

    2012-08-31

    We develop a classical density functional for water which combines the White Bear fundamental-measure theory (FMT) functional for the hard sphere fluid with attractive interactions based on the Statistical Associating Fluid Theory (SAFT-VR). This functional reproduces the properties of water at both long and short length scales over a wide range of temperatures, and is computationally efficient, comparable to the cost of FMT itself. We demonstrate our functional by applying it to systems composed of two hard rods, four hard rods arranged in a square and hard spheres in water.

  13. Preface: Special Topic on Advances in Density Functional Theory

    SciTech Connect (OSTI)

    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.

  14. Density Functional Theory with Dissipation: Transport through Single Molecules

    SciTech Connect (OSTI)

    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.

  15. Test Functions Space in Noncommutative Quantum Field Theory

    E-Print Network [OSTI]

    M. Chaichian; M. Mnatsakanova; A. Tureanu; Yu. Vernov

    2008-07-26

    It is proven that the $\\star$-product of field operators implies that the space of test functions in the Wightman approach to noncommutative quantum field theory is one of the Gel'fand-Shilov spaces $S^{\\beta}$ with $\\beta test functions smears the noncommutative Wightman functions, which are in this case generalized distributions, sometimes called hyperfunctions. The existence and determination of the class of the test function spaces in NC QFT is important for any rigorous treatment in the Wightman approach.

  16. Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    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

  17. Theory and applications of Bessel functions 

    E-Print Network [OSTI]

    Wasson, William Albert

    1949-01-01

    & o. Hence P~(&) (P P /, -&, ''') is a solution of Bessel's equation. I Next we shall define ? = & for A = & ? i ~" so that /" C~) V~ CX/ has a mean1ng when N 1s a negative integer. That J~(X) is now a solution of Bessel's equation even when 4...'s equation. Following custom we shall hereafter use 3&(&) to denote Bessel functions of any real order and reserve i7(&) t serve to denote functions of real integral order. 2. Recurrence Formulae for j?(X) . e olloring are the recurrence formulae...

  18. Development of Methods for Reducing the Cost of Density Functional Theory and Time-Dependent Density Functional Theory

    E-Print Network [OSTI]

    Hernandez, Samuel

    2015-01-01

    purified stochastic orbitals (pSO). TDsDFT approximates thefunction as an ensemble of pSO, which can be propagated0.5 ) [7] because fewer pSO orbitals are needed for larger

  19. (E)-2-[(2-Bromophenylimino)methyl]-5-methoxyphenol: X-ray and DFT-calculated structures

    SciTech Connect (OSTI)

    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.

  20. Density functional theory and optimal transportation with Coulomb cost

    E-Print Network [OSTI]

    Codina Cotar; Gero Friesecke; Claudia Klüppelberg

    2011-04-04

    We present here novel insight into exchange-correlation functionals in density functional theory, based on the viewpoint of optimal transport. We show that in the case of two electrons and in the semiclassical limit, the exact exchange-correlation functional reduces to a very interesting functional of novel form, which depends on an optimal transport map $T$ associated with a given density $\\rho$. Since the above limit is strongly correlated, the limit functional yields insight into electron correlations. We prove the existence and uniqueness of such an optimal map for any number of electrons and each $\\rho$, and determine the map explicitly in the case when $\\rho$ is radially symmetric.

  1. Improved association in a classical density functional theory for water

    E-Print Network [OSTI]

    Eric J. Krebs; Jeff B. Schulte; David Roundy

    2013-09-07

    We present a modification to our recently published SAFT-based classical density functional theory for water. We have recently developed and tested a functional for the averaged radial distribution function at contact of the hard-sphere fluid that is dramatically more accurate at interfaces than earlier approximations. We now incorporate this improved functional into the association term of our free energy functional for water, improving its description of hydrogen bonding. We examine the effect of this improvement by studying two hard solutes: a hard hydrophobic rod and a hard sphere. The improved functional leads to a moderate change in the density profile and a large decrease in the number of hydrogen bonds broken in the vicinity of the solutes.We present a modification to our recently published SAFT-based classical density functional theory for water. We have recently developed and tested a functional for the averaged radial distribution function at contact of the hard-sphere fluid that is dramatically more accurate at interfaces than earlier approximations. We now incorporate this improved functional into the association term of our free energy functional for water, improving its description of hydrogen bonding. We examine the effect of this improvement by studying two hard solutes: a hard hydrophobic rod and a hard sphere. The improved functional leads to a moderate change in the density profile and a large decrease in the number of hydrogen bonds broken in the vicinity of the solutes.

  2. Potential energy and free energy surfaces of glycyl-phenyalanyl-alanine (GFA) tripeptide: experiment and theory

    E-Print Network [OSTI]

    de Vries, Mattanjah S.

    energies of these complexes by means of density functional theory (DFT) and/or wave-function theory (WFT1 Potential energy and free energy surfaces of glycyl-phenyalanyl-alanine (GFA) tripeptide of Chemical Technology of Prague. Technicka 3, 166 28 Prague 6, Czech Republic. c) IRC Polymer and Complex

  3. Modeling Excited States in TiO2 Nanoparticles: On the Accuracy of a TD-DFT Based Description

    SciTech Connect (OSTI)

    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.

  4. Structure and Binding Site of Acetate on Pd(111) Determined Using Density Functional Theory and Low Energy Electron Diffraction

    E-Print Network [OSTI]

    Saldin, Dilano

    , University of Wisconsin ­ Milwaukee, Milwaukee, WI 53211, USA 4 National Energy Technology Laboratory and Low Energy Electron Diffraction Joanna James1 , Dilano K. Saldin2 , T. Zheng3 , W. T. Tysoe3 Theory (DFT) calculations have played a key role in the growing list of surface species whose structure

  5. Potassium-induced effect on structure and chemical activity of CuxO/Cu(111) (x?2) surface: A combined scanning tunneling microscopy and density functional theory study

    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

  6. A Computational Investigation of the Catalytic Properties of Graphene Oxide: Exploring Mechanisms Using DFT Methods

    E-Print Network [OSTI]

    Boukhvalov, Danil W; Bielawski, Christopher W; Son, Young-Woo

    2012-01-01

    Here we describe a computational study undertaken in an effort to elucidate the reaction mechanisms behind the experimentally observed oxidations and hydrations catalyzed by graphene oxide (GO). Using the oxidation of benzyl alcohol to benzaldehyde as a model reaction, density functional theory (DFT) calculations revealed that this reactivity stemmed from the transfer of hydrogen atoms from the organic molecule to the GO surface. In particular, neighbouring epoxide groups decorating GO's basal plane were ring-opened, resulting in the formation of diols, followed by dehydration. Consistent with the experimentally-observed dependence of this chemistry on molecular oxygen, our calculations revealed that the partially reduced catalyst was able to be recharged by molecular oxygen, allowing for catalyst turnover. Functional group-free carbon materials, such as graphite, were calculated to have substantially higher reaction barriers, indicating that the high chemical potential and rich functionality of GO are necess...

  7. Density functional theory for self-bound systems

    E-Print Network [OSTI]

    Nir Barnea

    2007-11-06

    The density functional theory is extended to account for self-bound systems. To this end the Hohenberg-Kohn theorem is formulated for the intrinsic density and a Kohn-Sham like procedure for an $N$--body system is derived using the adiabatic approximation to account for the center of mass motion.

  8. Monte Carlo tests of Orbital-Free Density Functional Theory

    E-Print Network [OSTI]

    D. I. Palade

    2014-12-12

    The relationship between the exact kinetic energy density in a quantum system in the frame of Density Functional Theory and the semiclassical functional expression for the same quantity is investigated. The analysis is performed with Monte Carlo simulations of the Kohn-Sham potentials. We find that the semiclassical form represents the statistical expectation value of the quantum nature. Based on the numerical results, we propose an empirical correction to the existing functional and an associated method to improve the Orbital-Free results.

  9. Spin projection with double hybrid density functional theory

    SciTech Connect (OSTI)

    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.

  10. Addressing spectroscopic quality of covariant density functional theory

    E-Print Network [OSTI]

    A. V. Afanasjev

    2014-09-17

    The spectroscopic quality of covariant density functional theory has been accessed by analyzing the accuracy and theoretical uncertainties in the description of spectroscopic observables. Such analysis is first presented for the energies of the single-particle states in spherical and deformed nuclei. It is also shown that the inclusion of particle-vibration coupling improves the description of the energies of predominantly single-particle states in medium and heavy-mass spherical nuclei. However, the remaining differences between theory and experiment clearly indicate missing physics and missing terms in covariant energy density functionals. The uncertainties in the predictions of the position of two-neutron drip line sensitively depend on the uncertainties in the prediction of the energies of the single-particle states. On the other hand, many spectroscopic observables in well deformed nuclei at ground state and finite spin only weakly depend on the choice of covariant energy density functional.

  11. Multi-time wave functions for quantum field theory

    SciTech Connect (OSTI)

    Petrat, Sören; 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 particle–position 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 Tomonaga–Schwinger representation and the Heisenberg picture in terms of operator-valued fields on space–time. 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 Tomonaga–Schwinger approach. •We show that they have a simple representation in terms of operator valued fields.

  12. Differentiable but exact formulation of density-functional theory

    SciTech Connect (OSTI)

    Kvaal, Simen Ekström, 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 density—in 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 Hohenberg–Kohn 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, Moreau–Yosida 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 (Fréchet) 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 Moreau–Yosida 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 Moreau–Yosida 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 Kohn–Sham theory is presented that does not suffer from the noninteracting representability problem in standard Kohn–Sham theory.

  13. Recent developments in classical density functional theory: Internal energy functional and diagrammatic structure of fundamental measure theory

    E-Print Network [OSTI]

    M. Schmidt; M. Burgis; W. S. B. Dwandaru; G. Leithall; P. Hopkins

    2012-12-27

    An overview of several recent developments in density functional theory for classical inhomogeneous liquids is given. We show how Levy's constrained search method can be used to derive the variational principle that underlies density functional theory. An advantage of the method is that the Helmholtz free energy as a functional of a trial one-body density is given as an explicit expression, without reference to an external potential as is the case in the standard Mermin-Evans proof by reductio ad absurdum. We show how to generalize the approach in order to express the internal energy as a functional of the one-body density distribution and of the local entropy distribution. Here the local chemical potential and the bulk temperature play the role of Lagrange multipliers in the Euler-Lagrange equations for minimiziation of the functional. As an explicit approximation for the free-energy functional for hard sphere mixtures, the diagrammatic structure of Rosenfeld's fundamental measure density unctional is laid out. Recent extensions, based on the Kierlik-Rosinberg scalar weight functions, to binary and ternary non-additive hard sphere mixtures are described.

  14. Relativistic density functional theory for finite nuclei and neutron stars

    E-Print Network [OSTI]

    J. Piekarewicz

    2015-02-05

    The main goal of the present contribution is a pedagogical introduction to the fascinating world of neutron stars by relying on relativistic density functional theory. Density functional theory provides a powerful--and perhaps unique--framework for the calculation of both the properties of finite nuclei and neutron stars. Given the enormous densities that may be reached in the core of neutron stars, it is essential that such theoretical framework incorporates from the outset the basic principles of Lorentz covariance and special relativity. After a brief historical perspective, we present the necessary details required to compute the equation of state of dense, neutron-rich matter. As the equation of state is all that is needed to compute the structure of neutron stars, we discuss how nuclear physics--particularly certain kind of laboratory experiments--can provide significant constrains on the behavior of neutron-rich matter.

  15. L-asparagine crystals with wide gap semiconductor features: Optical absorption measurements and density functional theory computations

    SciTech Connect (OSTI)

    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 Å, 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 2p–carboxyl, C 2p–side chain, and C 2p–carboxyl 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.

  16. Three Point Functions in the N=4 Orthogonal Coset Theory

    E-Print Network [OSTI]

    Changhyun Ahn; Hyunsu Kim; Jinsub Paeng

    2015-10-12

    We construct the lowest higher spin-2 current in terms of the spin-1 and the spin-1/2 currents living in the orthogonal SO(N+4)/[SO(N) x SO(4)] Wolf space coset theory for general N. The remaining fifteen higher spin currents are determined. We obtain the three-point functions of bosonic (higher) spin currents with two scalars for finite N and k (the level of the spin-1 current). By multiplying SU(2) x U(1) into the above Wolf space coset theory, the other fifteen higher spin currents together with the above lowest higher spin-2 current are realized in the extension of the large N=4 linear superconformal algebra. Similarly, the three-point functions of bosonic (higher) spin currents with two scalars for finite N and k are obtained. Under the large N 't Hooft limit, the two types of three-point functions in the nonlinear and linear versions coincide as in the unitary coset theory found previously.

  17. Three Point Functions in the N=4 Orthogonal Coset Theory

    E-Print Network [OSTI]

    Ahn, Changhyun; Paeng, Jinsub

    2015-01-01

    We construct the lowest higher spin-2 current in terms of the spin-1 and the spin-1/2 currents living in the orthogonal SO(N+4)/[SO(N) x SO(4)] Wolf space coset theory for general N. The remaining fifteen higher spin currents are determined. We obtain the three-point functions of bosonic (higher) spin currents with two scalars for finite N and k (the level of the spin-1 current). By multiplying SU(2) x U(1) into the above Wolf space coset theory, the other fifteen higher spin currents together with the above lowest higher spin-2 current are realized in the extension of the large N=4 linear superconformal algebra. Similarly, the three-point functions of bosonic (higher) spin currents with two scalars for finite N and k are obtained. Under the large N 't Hooft limit, the two types of three-point functions in the nonlinear and linear versions coincide as in the unitary coset theory found previously.

  18. Electronic structure of the heavy-fermion caged compound Ce?Pd??X? (X = Si, Ge) studied by density functional theory and photoelectron spectroscopy

    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 f¹more »(Ce³?) component. The spectral weight of f¹ 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

  19. Electronic structure of the heavy-fermion caged compound Ce3Pd20X6(X=Si,Ge) studied by density functional theory and photoelectron spectroscopy

    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 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 f¹more »(Ce³?) component. The spectral weight of f¹ 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

  20. Liquid drops on a surface: using density functional theory to calculate the binding potential and drop profiles and comparing with results from mesoscopic modelling

    E-Print Network [OSTI]

    Adam P. Hughes; Uwe Thiele; Andrew J. Archer

    2015-01-28

    The contribution to the free energy for a film of liquid of thickness $h$ on a solid surface, due to the interactions between the solid-liquid and liquid-gas interfaces is given by the binding potential, $g(h)$. The precise form of $g(h)$ determines whether or not the liquid wets the surface. Note that differentiating $g(h)$ gives the Derjaguin or disjoining pressure. We develop a microscopic density functional theory (DFT) based method for calculating $g(h)$, allowing us to relate the form of $g(h)$ to the nature of the molecular interactions in the system. We present results based on using a simple lattice gas model, to demonstrate the procedure. In order to describe the static and dynamic behaviour of non-uniform liquid films and drops on surfaces, a mesoscopic free energy based on $g(h)$ is often used. We calculate such equilibrium film height profiles and also directly calculate using DFT the corresponding density profiles for liquid drops on surfaces. Comparing quantities such as the contact angle and also the shape of the drops, we find good agreement between the two methods. We also study in detail the effect on $g(h)$ of truncating the range of the dispersion forces, both those between the fluid molecules and those between the fluid and wall. We find that truncating can have a significant effect on $g(h)$ and the associated wetting behaviour of the fluid.

  1. Particle-vibration coupling within covariant density functional theory

    E-Print Network [OSTI]

    E. Litvinova; P. Ring; V. Tselyaev

    2007-05-08

    Covariant density functional theory, which has so far been applied only within the framework of static and time dependent mean field theory is extended to include Particle-Vibration Coupling (PVC) in a consistent way. Starting from a conventional energy functional we calculate the low-lying collective vibrations in Relativistic Random Phase Approximation (RRPA) and construct an energy dependent self-energy for the Dyson equation. The resulting Bethe-Salpeter equation in the particle-hole ($ph$) channel is solved in the Time Blocking Approximation (TBA). No additional parameters are used and double counting is avoided by a proper subtraction method. The same energy functional, i.e. the same set of coupling constants, generates the Dirac-Hartree single-particle spectrum, the static part of the residual $ph$-interaction and the particle-phonon coupling vertices. Therefore a fully consistent description of nuclear excited states is developed. This method is applied for an investigation of damping phenomena in the spherical nuclei with closed shells $^{208}$Pb and $^{132}$Sn. Since the phonon coupling terms enrich the RRPA spectrum with a multitude of $ph\\otimes$phonon components a noticeable fragmentation of the giant resonances is found, which is in full agreement with experimental data and with results of the semi-phenomenological non-relativistic approach.

  2. Time-dependent localized Hartree-Fock density-functional linear response approach for photoionization of atomic excited states

    E-Print Network [OSTI]

    Chu, Shih-I

    Time-dependent localized Hartree-Fock density-functional linear response approach-dependent localized Hartree-Fock density-functional linear response approach for the treatment of photoionization, density-functional theory DFT com- bined with linear response approximation LRA 1,2 has been successfully

  3. Hole Localization in Molecular Crystals from Hybrid Density Functional Theory

    SciTech Connect (OSTI)

    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.

  4. First principles DFT investigation of yttrium-doped graphene: Electronic structure and hydrogen storage

    SciTech Connect (OSTI)

    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.

  5. The problem of the universal density functional and the density matrix functional theory

    SciTech Connect (OSTI)

    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.

  6. Daubechies wavelets for linear scaling density functional theory

    SciTech Connect (OSTI)

    Mohr, Stephan [Institut für Physik, Universität Basel, Klingelbergstr. 82, 4056 Basel (Switzerland); Univ. Grenoble Alpes, INAC-SP2M, F-38000 Grenoble, France and CEA, INAC-SP2M, F-38000 Grenoble (France); Ratcliff, Laura E.; Genovese, Luigi; Caliste, Damien; Deutsch, Thierry [Univ. Grenoble Alpes, INAC-SP2M, F-38000 Grenoble, France and CEA, INAC-SP2M, F-38000 Grenoble (France); Boulanger, Paul [Univ. Grenoble Alpes, INAC-SP2M, F-38000 Grenoble, France and CEA, INAC-SP2M, F-38000 Grenoble (France); Institut Néel, CNRS and Université Joseph Fourier, B.P. 166, 38042 Grenoble Cedex 09 (France); Goedecker, Stefan [Institut für Physik, Universität Basel, Klingelbergstr. 82, 4056 Basel (Switzerland)

    2014-05-28

    We demonstrate that Daubechies wavelets can be used to construct a minimal set of optimized localized adaptively contracted basis functions in which the Kohn-Sham orbitals can be represented with an arbitrarily high, controllable precision. Ground state energies and the forces acting on the ions can be calculated in this basis with the same accuracy as if they were calculated directly in a Daubechies wavelets basis, provided that the amplitude of these adaptively contracted basis functions is sufficiently small on the surface of the localization region, which is guaranteed by the optimization procedure described in this work. This approach reduces the computational costs of density functional theory calculations, and can be combined with sparse matrix algebra to obtain linear scaling with respect to the number of electrons in the system. Calculations on systems of 10?000 atoms or more thus become feasible in a systematic basis set with moderate computational resources. Further computational savings can be achieved by exploiting the similarity of the adaptively contracted basis functions for closely related environments, e.g., in geometry optimizations or combined calculations of neutral and charged systems.

  7. 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 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

  8. Electronic Structure of Ligated CdSe Clusters: Dependence on DFT Methodology

    SciTech Connect (OSTI)

    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.

  9. Phonons and related crystal properties from density-functional perturbation theory

    E-Print Network [OSTI]

    Wu, Zhigang

    -Functional Perturbation Theory 516 A. Lattice dynamics from electronic-structure theory 516 B. Density-functional theory July 2001) This article reviews the current status of lattice-dynamical calculations in crystals, using specialized topics are treated, including the implementation for metals, the calculation of the response

  10. Self-interaction corrections in density functional theory

    SciTech Connect (OSTI)

    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 Weizsäcker 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.

  11. NO Chemisorption on Cu/SSZ-13: a Comparative Study from Infrared Spectroscopy and DFT Calculations

    SciTech Connect (OSTI)

    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.

  12. Linear response time-dependent density functional theory for van der Waals coefficients

    E-Print Network [OSTI]

    Chu, Xi

    Linear response time-dependent density functional theory for van der Waals coefficients X. Chu Received 9 January 2004; accepted 15 June 2004 A linear response time-dependent density functional theory description of the linear response function and of the induced self- consistent field, which adequately

  13. Spin-Multiplet Energies from Time-Dependent Density-Functional Theory

    E-Print Network [OSTI]

    Gross, E.K.U.

    Spin-Multiplet Energies from Time-Dependent Density-Functional Theory M. Petersilka and E excitation energies, we develop a density-functional method for the calculation of excitation energies energies which is based on time-dependent density- functional theory (TDDFT) [26]. In the linear response

  14. Symmetry-adapted perturbation theory with Kohn-Sham orbitals using non-empirically tuned, long-range-corrected density functionals

    SciTech Connect (OSTI)

    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.

  15. Systematic approach for simultaneously correcting the band-gap andp-dseparation errors of common cation III-V or II-VI binaries in density functional theory calculations within a local density approximation

    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

  16. Methanol Synthesis from CO2 Hydrogenation over a Pd4/In2O3 Model Catalyst: A Combined DFT and Kinetic Study

    SciTech Connect (OSTI)

    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.

  17. Supplementary data for "Relativistic density functional theory modeling of plutonium and

    E-Print Network [OSTI]

    Titov, Anatoly

    Supplementary data for "Relativistic density functional theory modeling of plutonium and americium equilibrium geometries of plutonium and americium oxide molecules (standard .xyz files separated by empty

  18. Reaction dynamics study of O{sup -}+C{sub 2}H{sub 2} with crossed beams and density-functional theory calculations

    SciTech Connect (OSTI)

    Liu Li; Li Yue; Farrar, James M. [Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)

    2005-09-01

    The reactions between O{sup -} and C{sub 2}H{sub 2} have been studied using the crossed-beam technique and density-functional theory (DFT) calculations in the collision energy range from 0.35 to 1.5 eV (34-145 kJ/mol). Both proton transfer and C-O bond formation are observed. The proton transfer channel forming C{sub 2}H{sup -} is the dominant pathway. The center-of-mass flux distributions of the C{sub 2}H{sup -} product ions are highly asymmetric, with maxima close to the velocity and direction of the precursor acetylene beam, characteristic of direct reactions. The reaction quantitatively transforms the entire reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the proton is transferred in a configuration in which both the breaking and the forming bonds are extended. The C-O bond formation channel producing HC{sub 2}O{sup -} displays a distinctive kinematic picture in which the product distribution switches from predominantly forward scattering with a weak backward peak to sideways scattering as the collision energy increases. At low collision energies, the reaction occurs through an intermediate that lives a significant fraction of a rotational period. The asymmetry in the distribution leads to a lifetime estimate of 600 fs, in reasonable agreement with DFT calculations showing that hydrogen-atom migration is rate limiting. At higher collision energies, the sideways-scattered products arise from repulsive energy release from a bent transition state.

  19. Numerical Solution of 3D Poisson-Nernst-Planck Equations Coupled with Classical Density Functional Theory for Modeling Ion and Electron Transport in a Confined Environment

    SciTech Connect (OSTI)

    Meng, Da; Zheng, Bin; Lin, Guang; Sushko, Maria L.

    2014-08-29

    We have developed efficient numerical algorithms for the solution of 3D steady-state Poisson-Nernst-Planck equations (PNP) with excess chemical potentials described by the classical density functional theory (cDFT). The coupled PNP equations are discretized by finite difference scheme and solved iteratively by Gummel method with relaxation. The Nernst-Planck equations are transformed into Laplace equations through the Slotboom transformation. Algebraic multigrid method is then applied to efficiently solve the Poisson equation and the transformed Nernst-Planck equations. A novel strategy for calculating excess chemical potentials through fast Fourier transforms is proposed which reduces computational complexity from O(N2) to O(NlogN) where N is the number of grid points. Integrals involving Dirac delta function are evaluated directly by coordinate transformation which yields more accurate result compared to applying numerical quadrature to an approximated delta function. Numerical results for ion and electron transport in solid electrolyte for Li ion batteries are shown to be in good agreement with the experimental data and the results from previous studies.

  20. Basic Theory in Construction of Boolean Functions with Maximum Possible Annihilator Immunity

    E-Print Network [OSTI]

    International Association for Cryptologic Research (IACR)

    Basic Theory in Construction of Boolean Functions with Maximum Possible Annihilator Immunity #3. In this paper we present a construction keeping in mind the basic theory of annihilator immunity the basic theory. Most importantly, the cryptographic properties of our constructions, such as nonlinearity

  1. Basic Theory in Construction of Boolean Functions with Maximum Possible Annihilator Immunity

    E-Print Network [OSTI]

    International Association for Cryptologic Research (IACR)

    Basic Theory in Construction of Boolean Functions with Maximum Possible Annihilator Immunity Deepak present a construction keeping in mind the basic theory of annihilator immunity. This construction immunity that comes from the basic theory. Most importantly, the cryptographic properties of our

  2. Department for Analysis and Computational Number Theory Additive functions and number systems

    E-Print Network [OSTI]

    Department for Analysis and Computational Number Theory Additive functions and number systems systems April 7, 2010 1 / 35 #12;Department for Analysis and Computational Number Theory Outline Number and Computational Number Theory Number systems Let R be an integral domain, b R, and N = {n1, . . . , nm} R

  3. Density-Functional Theory and Quantum Chemistry Studies on "dry" and "wet"

    E-Print Network [OSTI]

    Alavi, Ali

    Density-Functional Theory and Quantum Chemistry Studies on "dry" and "wet" NaCl(001) vorgelegt von essential role as a food preserva- tive. However, many fundamental physical and chemical properties of Na), and defects on NaCl(001) surfaces have been examined with density-functional theory within the plane

  4. Band structures Optical absorption Summary Key concepts in Density Functional Theory (II)

    E-Print Network [OSTI]

    Botti, Silvana

    Band structures Optical absorption Summary Key concepts in Density Functional Theory (II) Kohn-Sham scheme, band structure and optical spectra Silvana Botti European Theoretical Spectroscopy Facility (ETSF, Belfast Key concepts in Density Functional Theory (II) Silvana Botti #12;Band structures Optical

  5. Electronvibration coupling in time-dependent density-functional theory: Application to benzene

    E-Print Network [OSTI]

    Bertsch George F.

    Electron­vibration coupling in time-dependent density-functional theory: Application to benzene G://jcp.aip.org/about/rights_and_permissions #12;Electron­vibration coupling in time-dependent density-functional theory: Application to benzene G for electron­vibration coupling, we apply it to the optical properties of the ­ * transitions in benzene

  6. Supplementary material to "Curvature and frontier orbital energies in density functional theory", by Stein et al.

    E-Print Network [OSTI]

    Baer, Roi

    Supplementary material to "Curvature and frontier orbital energies in density functional theory: [{ }] [{ }] #12;Supplementary material to "Curvature and frontier orbital energies in density functional theory the average curvature. This relation is Eq. (8) in the paper. #12;Supplementary material to "Curvature

  7. Evaluations of certain theta functions in Ramanujan theory of alternative modular bases

    E-Print Network [OSTI]

    N. D. Bagis

    2015-11-11

    We give evaluations of certain Borwein's theta functions which appear in Ramanujan theory of alternative elliptic modular bases. Most of this theory where developed by B.C. Berndt, S. Bhargava and F.G. Garvan. We also study the most general class of these theta functions and give evaluation conjectures.

  8. Time-dependent Internal DFT formalism and Kohn-Sham scheme

    E-Print Network [OSTI]

    J. Messud

    2009-11-05

    We generalize to the time-dependent case the stationary Internal DFT / Kohn-Sham formalism presented in Ref. [14]. We prove that, in the time-dependent case, the internal properties of a self-bound system (as an atomic nuclei) are all defined by the internal one-body density and the initial state. We set-up a time-dependent Internal Kohn-Sham scheme as a practical way to compute the internal density. The main difference with the traditional DFT / Kohn-Sham formalism is the inclusion of the center-of-mass correlations in the functional.

  9. Dynamics study of the reaction OH{sup -}+C{sub 2}H{sub 2}{yields}C{sub 2}H{sup -}+H{sub 2}O with crossed beams and density-functional theory calculations

    SciTech Connect (OSTI)

    Liu Li; Li Yue; Farrar, James M. [Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)

    2006-03-28

    The proton transfer reaction between OH{sup -} and C{sub 2}H{sub 2}, the sole reactive process observed over the collision energy range from 0.37 to 1.40 eV, has been studied using the crossed beam technique and density-functional theory (DFT) calculations. The center of mass flux distributions of the product C{sub 2}H{sup -} ions at three different energies are highly asymmetric, characteristic of a direct process occurring on a time scale much less than a rotational period of any transient intermediate. The maxima in the flux distributions correspond to product velocities and directions close to those of the precursor acetylene reactants. The reaction quantitatively transforms the entire exothermicity into internal excitation of the products, consistent with an energy release motif in which the proton is transferred early, in a configuration in which the forming bond is extended. This picture is supported by DFT calculations showing that the first electrostatically bound intermediate on the reaction pathway is the productlike C{sub 2}H{sup -}{center_dot}H{sub 2}O species. Most of the incremental translational energy in the two higher collision energy experiments appears in product translational energy, and provides an example of induced repulsive energy release characteristic of the heavy+light-heavy mass combination.

  10. Magnetic and antimagnetic rotation in covariant density functional theory

    SciTech Connect (OSTI)

    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.

  11. Element orbitals for Kohn-Sham density functional theory

    SciTech Connect (OSTI)

    Lin, Lin; Ying, Lexing

    2012-05-08

    We present a method to discretize the Kohn-Sham Hamiltonian matrix in the pseudopotential framework by a small set of basis functions automatically contracted from a uniform basis set such as planewaves. Each basis function is localized around an element, which is a small part of the global domain containing multiple atoms. We demonstrate that the resulting basis set achieves meV accuracy for 3D densely packed systems with a small number of basis functions per atom. The procedure is applicable to insulating and metallic systems.

  12. Switched nonlinear differential algebraic equations: Solution theory, Lyapunov functions, and stability$

    E-Print Network [OSTI]

    Trenn, Stephan

    Switched nonlinear differential algebraic equations: Solution theory, Lyapunov functions¨urzburg, Germany Abstract We study switched nonlinear differential algebraic equations (DAEs) with respect in earlier work for linear switched DAEs to establish a solution framework for switched nonlinear DAEs

  13. An Information Systems Security Risk Assessment Model Under Dempster- Schafer Theory of Belief Functions

    E-Print Network [OSTI]

    Sun, Lili; Srivastava, Rajendra P.; Mock, Theodore J.

    2006-01-01

    This study develops an alternative methodology for the risk analysis of information systems security (ISS), an evidential reasoning approach under the Dempster-Shafer theory of belief functions. The approach has the following important dimensions...

  14. Semiparametric functional data analysis for longitudinal/clustered data: theory and application 

    E-Print Network [OSTI]

    Hu, Zonghui

    2006-04-12

    : Statistics iii ABSTRACT Semiparametric Functional Data Analysis for Longitudinal/Clustered Data: Theory and Application. (December 2004) Zonghui Hu, B.S., Dalian University of Technology, Dalian, P.R.China; M.S., Dalian University of Technology, Dalian, P...

  15. Joint inversion of receiver function and ambient noise based on Bayesian theory

    E-Print Network [OSTI]

    van der Hilst, Robert D.

    In this study, we present a method for the joint inversion of receiver function and ambient noise based on Bayesian inverse theory (Tarantola, 1987, 2005). The nonlinear inversion method of the complex spectrum ratio of ...

  16. Published: April 05, 2011 r 2011 American Chemical Society 1296 dx.doi.org/10.1021/ct100607w |J. Chem. Theory Comput. 2011, 7, 12961306

    E-Print Network [OSTI]

    Herbert, John

    43210, United States bS Supporting Information ABSTRACT: The electronic spectrum of alternant polycyclic-dependent density functional theory (TD-DFT) affords reasonable excitation energies for the 1 Lb state in such molecules, but often severely underestimates 1 La excitation energies and fails to reproduce observed trends

  17. PHYSICAL REVIEW C 74, 034301 (2006) Effective quadrupole-quadrupole interaction from density functional theory

    E-Print Network [OSTI]

    Bertsch George F.

    2006-01-01

    called density functional theory,1 and the other is the configuration-interaction shell-model (CISM energies, and the treatment of excitations requires extensions of the theory. In contrast, the CISM gives] proposed to use the SCMF to determine the single-particle Hamiltonian of the CISM so as to gain

  18. The three point function in Liouville and $\\mathcal{N}=1$ Super Liouville Theory

    E-Print Network [OSTI]

    Tupia, Martín D Arteaga

    2015-01-01

    In this dissertation we present some basic features about Liouville and $\\mathcal{N}=1$ Super Liouville Theory, and focus in the computation of their three point functions. Additionally, we include an introduction to Conformal Field Theories (CFT) and Supersymmetry, which are the basic tools of the present research.

  19. The three point function in Liouville and $\\mathcal{N}=1$ Super Liouville Theory

    E-Print Network [OSTI]

    Martín D. Arteaga Tupia

    2015-08-20

    In this dissertation we present some basic features about Liouville and $\\mathcal{N}=1$ Super Liouville Theory, and focus in the computation of their three point functions. Additionally, we include an introduction to Conformal Field Theories (CFT) and Supersymmetry, which are the basic tools of the present research.

  20. Double-Pole Approximation in Time-Dependent Density Functional Theory

    E-Print Network [OSTI]

    Gross, E.K.U.

    Double-Pole Approximation in Time-Dependent Density Functional Theory H. Appel and E.K.U. Gross-dependent density func- tional theory (TDDFT) is given. This extends the single-pole approximation (SPA) to two strongly- coupled poles. The analysis provides both an illustration of how TDDFT works when strong exchange

  1. Structural, elastic, electronic and phonon properties of SnX{sub 2}O{sub 4} (X=Mg, Zn, Cd) spinel from density functional theory

    SciTech Connect (OSTI)

    U?ur, Gökay; 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.

  2. Spin-orbit relativistic long-range corrected time-dependent density functional theory for investigating spin-forbidden transitions in photochemical reactions

    SciTech Connect (OSTI)

    Nakata, Ayako; Tsuneda, Takao; Hirao, Kimihiko [Advanced Science Institute, RIKEN, Wako 351-0198 (Japan); CREST, Japan Science and Technology Agency, Kawaguchi 332-0012 (Japan)

    2011-12-14

    A long-range corrected (LC) time-dependent density functional theory (TDDFT) incorporating relativistic effects with spin-orbit couplings is presented. The relativistic effects are based on the two-component zeroth-order regular approximation Hamiltonian. Before calculating the electronic excitations, we calculated the ionization potentials (IPs) of alkaline metal, alkaline-earth metal, group 12 transition metal, and rare gas atoms as the minus orbital (spinor) energies on the basis of Koopmans' theorem. We found that both long-range exchange and spin-orbit coupling effects are required to obtain Koopmans' IPs, i.e., the orbital (spinor) energies, quantitatively in DFT calculations even for first-row transition metals and systems containing large short-range exchange effects. We then calculated the valence excitations of group 12 transition metal atoms and the Rydberg excitations of rare gas atoms using spin-orbit relativistic LC-TDDFT. We found that the long-range exchange and spin-orbit coupling effects significantly contribute to the electronic spectra of even light atoms if the atoms have low-lying excitations between orbital spinors of quite different electron distributions.

  3. Valence excitation energies of alkenes, carbonyl compounds, and azabenzenes by time-dependent density functional theory: Linear response

    E-Print Network [OSTI]

    Truhlar, Donald G

    -dependent density functional theory: Linear response of the ground state compared to collinear and noncollinear spin, carbonyl compounds, and azabenzenes by time-dependent density functional theory: Linear response; accepted 13 March 2013; published online 3 April 2013) Time-dependent density functional theory (TDDFT

  4. Density-functional theory of freezing of quantum liquids at zero temperature using exact liquid-state linear response

    E-Print Network [OSTI]

    Likos, Christos N.

    Density-functional theory of freezing of quantum liquids at zero temperature using exact liquid-functional theory to study the freezing of superfluid 4 He, charged bosons, and charged fermions at zero temperature-functional theory of freezing that involve linear response, all fail to correctly describe the crystalliza- tion

  5. A density functional theory study of hydroxyl and the intermediate in the water formation reaction on Pt

    E-Print Network [OSTI]

    Alavi, Ali

    A density functional theory study of hydroxyl and the intermediate in the water formation reaction: Wed, 28 Jan 2015 16:19:40 #12;A density functional theory study of hydroxyl and the intermediate functional theory has been used to study the adsorption of hydroxyl at low and high coverages and also

  6. On the accuracy of density-functional theory exchange-correlation functionals for H bonds in small water clusters. II. The water hexamer

    E-Print Network [OSTI]

    Alavi, Ali

    On the accuracy of density-functional theory exchange-correlation functionals for H bonds in small for hydro- gen H bonds? What is the best exchange-correlation xc functional for treating H bonds? Questions

  7. A Theory of Linear Fractional Transformations of Rational Functions

    E-Print Network [OSTI]

    Reiter, Harold

    functions, we say that g g if g = ax+b cx+d -1 g ax+b cx+d , where a b c d = 0. For practical purposes ax+b cx+d = ax + b, a linear function, our methods yield a large number of first level invariants and n i=0 Aixi and n i=0 Bixi have no roots in common. Also, g g if g = ax+b cx+d -1 g ax+b cx

  8. Theory and Application of Linear Supply Function Equilibrium in Electricity Markets

    E-Print Network [OSTI]

    Baldick, Ross

    Theory and Application of Linear Supply Function Equilibrium in Electricity Markets Ross Baldick Department of Electrical and Computer Engineering, The University of Texas at Austin, 1 University Station C equilibrium (SFE) model of interaction in an electricity market. We assume a linear demand function

  9. Density Functional Theory for Protein Transfer Free Energy Eric A. Mills and Steven S. Plotkin*

    E-Print Network [OSTI]

    Plotkin, Steven S.

    Density Functional Theory for Protein Transfer Free Energy Eric A. Mills and Steven S. Plotkin ABSTRACT: We cast the problem of protein transfer free energy within the formalism of density functional excluded volume, solvent-accessible surface area, and temperature dependence of the transfer free energy

  10. Dispersion-correcting potentials can significantly improve the bond dissociation enthalpies and noncovalent binding energies predicted by density-functional theory

    SciTech Connect (OSTI)

    DiLabio, Gino A., E-mail: Gino.DiLabio@nrc.ca [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada); Department of Chemistry, University of British Columbia, Okanagan, 3333 University Way, Kelowna, British Columbia V1V 1V7 (Canada); Koleini, Mohammad [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada) [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada); Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4 (Canada)

    2014-05-14

    Dispersion-correcting potentials (DCPs) are atom-centered Gaussian functions that are applied in a manner that is similar to effective core potentials. Previous work on DCPs has focussed on their use as a simple means of improving the ability of conventional density-functional theory methods to predict the binding energies of noncovalently bonded molecular dimers. We show in this work that DCPs developed for use with the LC-?PBE functional along with 6-31+G(2d,2p) basis sets are capable of simultaneously improving predicted noncovalent binding energies of van der Waals dimer complexes and covalent bond dissociation enthalpies in molecules. Specifically, the DCPs developed herein for the C, H, N, and O atoms provide binding energies for a set of 66 noncovalently bonded molecular dimers (the “S66” set) with a mean absolute error (MAE) of 0.21 kcal/mol, which represents an improvement of more than a factor of 10 over unadorned LC-?PBE/6-31+G(2d,2p) and almost a factor of two improvement over LC-?PBE/6-31+G(2d,2p) used in conjunction with the “D3” pairwise dispersion energy corrections. In addition, the DCPs reduce the MAE of calculated X-H and X-Y (X,Y = C, H, N, O) bond dissociation enthalpies for a set of 40 species from 3.2 kcal/mol obtained with unadorned LC-?PBE/6-31+G(2d,2p) to 1.6 kcal/mol. Our findings demonstrate that broad improvements to the performance of DFT methods may be achievable through the use of DCPs.

  11. Molecular Density Functional Theory for water with liquid-gas coexistence and correct pressure

    E-Print Network [OSTI]

    Jeanmairet, Guillaume; Sergiievskyi, Volodymyr; Borgis, Daniel

    2015-01-01

    The solvation of hydrophobic solutes in water is special because liquid and gas are almost at coexistence. In the common hypernetted chain approximation to integral equations, or equivalently in the homogenous reference fluid of molecular density functional theory, coexistence is not taken into account. Hydration structures and energies of nanometer-scale hydrophobic solutes are thus incorrect. In this article, we propose a bridge functional that corrects this thermodynamic inconsistency by introducing a metastable gas phase for the homogeneous solvent. We show how this can be done by a third order expansion of the functional around the bulk liquid density that imposes the right pressure and the correct second order derivatives. Although this theory is not limited to water, we apply it to study hydrophobic solvation in water at room temperature and pressure and compare the results to all-atom simulations. With this correction, molecular density functional theory gives, at a modest computational cost, quantita...

  12. Fluid - solid transition in simple systems using density functional theory

    E-Print Network [OSTI]

    Atul S. Bharadwaj; Yashwant Singh

    2014-11-24

    A free energy functional for a crystal proposed by Singh and Singh (Europhysics Letters \\textbf{88}, 16005 (2009)) which contains both the symmetry-conserved and symmetry-broken parts of the direct pair correlation function has been used to investigate the fluid-solid transition in systems interacting via purely repulsive WCA Lennard - Jones (RLJ) potential and the full Lennard - Jones (LJ) potential. The results found for freezing parameters for the fluid - face centred cubic (fcc) crystal transition are in very good agreement with simulation results. It is shown that although the contribution made by the symmetry broken part to the grand thermodynamic potential at the freezing point is small compared to that of the symmetry conserving part, its role is crucial in stabilizing the crystalline structure and on values of freezing parameters. The effect of attractive part of the LJ potential on the freezing parameters is found to be small, confirming the view that the fluid - solid transition is primarily determined by the repulsive part of the potential.

  13. Glueball Wave Functions in U(1) Lattice Gauge Theory

    E-Print Network [OSTI]

    Mushtaq Loan; Yi Ying

    2006-06-26

    Standard Monte Carlo simulations have been performed for 3-dimensional U(1) lattice gauge model on improved lattices to measure the wavefunction and size of the scalar and the tensor glueballs. Our results show the radii of ~ 0.60 and ~ 1.12 in the units of string tension, or ~0.28 and ~0.52 fm, for the scalar and tensor glueballs, respectively. At finite temperature we see clear evidence of the deconfined phase, and the transition appears to be similar to that of the two-dimensional XY model as expected from universality arguments. Preliminary results show no significant changes in the glueball wave functions and the masses in the deconfined phase.

  14. Determining Relative f and d Orbital Contributions to M?Cl Covalency in MCl62– (M = Ti, Zr, Hf, U) and UOCl5 Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory

    SciTech Connect (OSTI)

    Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Clark, David L.; Conradson, Steven D.; Kozimor, Stosh A.; Martin, Richard L.; Schwarz, Daniel E.; Shuh, David K.; Wagner, Gregory L.; Wilkerson, Marianne P.; Wolfsberg, Laura E.; Yang, Ping

    2012-03-09

    Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe electronic structure for O{sub h}-MCl{sub 6}{sup 2-}(M = Ti, Zr, Hf, U) and C{sub 4v}-UOCl{sub 5}{sup -}, and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl{sub 6}{sup 2-}. For the MCl{sub 6}{sup 2-}, where transitions into d orbitals of t{sub 2g} symmetry are spectroscopically resolved for all four complexes, the experimentally determined Cl 3p character per M-Cl bond increases from 8.3(4)% (TiCl{sub 6}{sup 2-}) to 10.3(5)% (ZrCl{sub 6}{sup 2-}), 12(1)% (HfCl{sub 6}{sup 2-}), and 26 18(1)% (UCl{sub 6}{sup 2-}). Chlorine K-edge XAS spectra of UOCl{sub 5}{sup -} provide additional insights into the transition assignments by 27 lowering the symmetry to C{sub 4v}, where five pre-edge transitions into both 5f and 6d orbitals are observed. For UCl{sub 6}{sup 2-}, the XAS data 28 suggest that orbital mixing associated with the U 5f orbitals is considerably lower than that of the U 6d orbitals. For both UCl{sub 6}{sup 2-}29 and UOCl{sub 5}{sup -}, the ground-state DFT calculations predict a larger 5f contribution to bonding than is determined experimentally. 30 These findings are discussed in the context of conventional theories of covalent bonding for d- and f-block metal complexes.

  15. Effective field theory for dilute fermions with pairing

    SciTech Connect (OSTI)

    Furnstahl, R.J. [Department of Physics, Ohio State University, Columbus, OH 43210 (United States)], E-mail: furnstahl.1@osu.edu; Hammer, H.-W. [Helmholtz-Institut fuer Strahlen- und Kernphysik (Theorie), Universitaet Bonn, Nussallee 14-16, D-53115 Bonn (Germany)], E-mail: hammer@itkp.uni-bonn.de; Puglia, S.J. [SBIG PLC, Berkeley Square House, London W1J 6BR (United Kingdom)], E-mail: spuglia@sbiguk.com

    2007-11-15

    Effective field theory (EFT) methods for a uniform system of fermions with short-range, natural interactions are extended to include pairing correlations, as part of a program to develop a systematic Kohn-Sham density functional theory (DFT) for medium and heavy nuclei. An effective action formalism for local composite operators leads to a free-energy functional that includes pairing by applying an inversion method order by order in the EFT expansion. A consistent renormalization scheme is demonstrated for the uniform system through next-to-leading order, which includes induced-interaction corrections to pairing.

  16. Gedanken densities and exact constraints in density functional theory

    SciTech Connect (OSTI)

    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.

  17. One-Loop Partition Functions in Deformed $\\mathcal{N}=4$ SYM Theory

    E-Print Network [OSTI]

    Jan Fokken; Matthias Wilhelm

    2015-03-26

    We study the thermodynamic behaviour of the real $\\beta$- and $\\gamma_i$-deformation of $\\mathcal{N}=4$ Super Yang-Mills theory on $\\mathbb{R}\\times S^3$ in the planar limit. These theories were shown to be the most general asymptotically integrable supersymmetric and non-supersymmetric field-theory deformations of $\\mathcal{N}=4$ Super Yang-Mills theory, respectively. We calculate the first loop correction to their partition functions using an extension of the dilatation-operator and P\\'{o}lya-counting approach. In particular, we account for the one-loop finite-size effects which occur for operators of length one and two. Remarkably, we find that the $\\mathcal{O}(\\lambda)$ correction to the Hagedorn temperature is independent of the deformation parameters, although the partition function depends on them in a non-trivial way.

  18. Exact relations of the quasienergy functional and the exchange-correlation potential from the Floquet formulation of time-dependent density functional theory

    E-Print Network [OSTI]

    Telnov, Dmitry A.; Chu, Shih-I

    2000-12-13

    In the framework of the Floquet formulation of time-dependent density functional theory we present several exact relations involving different parts of the quasienergy functional. These relations hold when the exact densities ...

  19. 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

  20. Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory

    SciTech Connect (OSTI)

    Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.; Boland, Kevin S.; Burns, Carol J.; Clark, David L.; Conradson, Steven D.; Martin, Richard L.; Wikerson, Marianne P.; Wolfsberg, Laura E.

    2009-09-02

    We describe the use of Cl K-edge X-ray Absorption Spectroscopy (XAS) and both ground state and time-dependent hybrid density functional theory (DFT) to probe electronic structure and determine the degree of orbital mixing in M-Cl bonds for (C5Me5)2MCl2 (M = Ti, 1; Zr, 2; Hf, 3; Th, 4; and U, 5), where we can directly compare a class of structurally similar compounds for d- and f-elements. We report direct experimental evidence for covalency in M-Cl bonding, including actinides, and offer insight into the relative roles of the valence f- and dorbitals in these systems. The Cl K-edge XAS data for the group IV transition metals, 1 – 3, show slight decreases in covalency in M-Cl bonding with increasing principal quantum number, in the order Ti > Zr > Hf. The percent Cl 3p character per M-Cl bond was experimentally determined to be 25, 23, and 22% per M-Cl bond for 1-3, respectively. For actinides, we find a shoulder on the white line for (C5Me5)2ThCl2, 4, and distinct, but weak pre-edge features for 2 (C5Me5)2UCl2, 5. The percent Cl 3p character in Th-Cl bonds in 4 was determined to be 14 %, with high uncertainty, while the U-Cl bonds in 5 contains 9 % Cl 3p character. The magnitudes of both values are approximately half what was observed for the transition metal complexes in this class of bent metallocene dichlorides. Using the hybrid DFT calculations as a guide to interpret the experimental Cl K-edge XAS, these experiments suggest that when evaluating An- Cl bonding, both 5f- and 6d-orbitals should be considered. For (C5Me5)2ThCl2, the calculations and XAS indicate that the 5f- and 6d-orbitals are nearly degenerate and heavily mixed. In contrast, the 5f- and 6d-orbitals in (C5Me5)2UCl2 are no longer degenerate, and fall in two distinct energy groupings. The 5f-orbitals are lowest in energy and split into a 5-over-2 pattern with the high lying U 6d-orbitals split in a 4-over-1 pattern, the latter of which is similar to the dorbital splitting in group IV transition metal (C5R5)2MCl2 (R = H, Me) compounds. Time dependent-DFT (TD-DFT) was used to calculate the energies and intensities of Cl 1s transitions into empty metal based orbitals containing Cl 3p character, and provide simulated Cl K-edge XAS spectra for 1 - 4. However, for 5, which has two unpaired electrons, analogous information was obtained from transition dipole calculations using ground state Kohn-Sham orbitals. The simulations provide additional confidence in the interpretation of spectra based on ground state calculations. Overall, this study demonstrates that Cl K-edge XAS and DFT calculations represent powerful tools that can be used to evaluate electronic structure and covalency in actinide metal-ligand bonding. In addition, these results provide a framework that can be used in future studies to evaluate actinide covalency in compounds that contain transuranic elements.

  1. Geometry of Spin and Spin^c structures in the M-theory partition function

    E-Print Network [OSTI]

    Hisham Sati

    2012-04-01

    We study the effects of having multiple Spin structures on the partition function of the spacetime fields in M-theory. This leads to a potential anomaly which appears in the eta-invariants upon variation of the Spin structure. The main source of such spaces are manifolds with nontrivial fundamental group, which are also important in realistic models. We extend the discussion to the Spin^c case and find the phase of the partition function, and revisit the quantization condition for the C-field in this case. In type IIA string theory in ten dimensions, the mod 2 index of the Dirac operator is the obstruction to having a well-defined partition function. We geometrically characterize manifolds with and without such an anomaly and extend to the case of nontrivial fundamental group. The lift to KO-theory gives the alpha-invariant, which in general depends on the Spin structure. This reveals many interesting connection to positive scalar curvature manifolds and constructions related to the Gromov-Lawson-Rosenberg conjecture. In the twelve-dimensional theory bounding M-theory, we study similar geometric questions, including choices of metrics and obtaining elements of K-theory in ten dimensions by pushforward in K-theory on the disk fiber. We interpret the latter in terms of the families index theorem for Dirac operators on the M-theory circle and disk. This involves superconnections, eta-forms, and infinite-dimensional bundles, and gives elements in Deligne cohomology in lower dimensions. We illustrate our discussion with many examples throughout.

  2. Four-point correlation function of stress-energy tensors in N=4 superconformal theories

    E-Print Network [OSTI]

    G. P. Korchemsky; E. Sokatchev

    2015-09-24

    We derive the explicit expression for the four-point correlation function of stress-energy tensors in four-dimensional N=4 superconformal theory. We show that it has a remarkably simple and suggestive form allowing us to predict a large class of four-point correlation functions involving the stress-energy tensor and other conserved currents. We then apply the obtained results on the correlation functions to computing the energy-energy correlations, which measure the flow of energy in the final states created from the vacuum by a source. We demonstrate that they are given by a universal function independent of the choice of the source. Our analysis relies only on N=4 superconformal symmetry and does not use the dynamics of the theory.

  3. Linear relations among 4-point functions in the high energy limit of string theory

    E-Print Network [OSTI]

    Pei-Ming Ho; Xue-Yan Lin

    2006-05-30

    The decoupling of zero-norm states leads to linear relations among 4-point functions in the high energy limit of string theory. Recently it was shown that the linear relations uniquely determine ratios among 4-point functions at the leading order. The purpose of this paper is to extend the validity of the same approach to the next-to-leading order and higher orders.

  4. Superconformal field theory in three dimensions: Correlation functions of conserved currents

    E-Print Network [OSTI]

    Evgeny I. Buchbinder; Sergei M. Kuzenko; Igor B. Samsonov

    2015-07-01

    For N-extended superconformal field theories in three spacetime dimensions (3D), with N=1,2,3, we compute the two- and three-point correlation functions of the supercurrent and the flavour current multiplets. We demonstrate that supersymmetry imposes additional restrictions on the correlators of conserved currents as compared with the non-supersymmetric case studied by Osborn and Petkou in hep-th/9307010. It is shown that the three-point function of the supercurrent is determined by a single functional form consistent with the conservation equation and all the symmetry properties. Similarly, the three-point function of the flavour current multiplets is also determined by a single functional form in the N=1 and N=3 cases. The specific feature of the N=2 case is that two independent structures are allowed for the three-point function of flavour current multiplets, but only one of them contributes to the three-point function of the conserved currents contained in these multiplets. Since the supergravity and super-Yang-Mills Ward identities are expected to relate the coefficients of the two- and three-point functions under consideration, the results obtained for 3D superconformal field theory are analogous to those in 2D conformal field theory. In addition, we present a new supertwistor construction for compactified Minkowski superspace. It is suitable for developing superconformal field theory on 3D spacetimes other than Minkowski space, such as S^1 x S^2 and its universal covering space R x S^2.

  5. Isospin coupling-channel decomposition of nuclear symmetry energy in covariant density functional theory

    E-Print Network [OSTI]

    Qian Zhao; Bao Yuan Sun; Wen Hui Long

    2014-11-23

    The isospin coupling-channel decomposition of the potential energy density functional is carried out within the covariant density functional theory, and their isospin and density dependence in particular the influence on the symmetry energy is studied. It is found that both isospin-singlet and isospin-triplet components of the potential energy play the dominant role in deciding the symmetry energy, especially when the Fock diagram is introduced. The results illustrate a quite different mechanism to the origin of the symmetry energy from the microscopic Brueckner-Hartree-Fock theory, and demonstrate the importance of the Fork diagram in the CDF theory, especially from the isoscalar mesons, in the isospin properties of the in-medium nuclear force at high density.

  6. Linear Algebraic Calculation of Green's function for Large-Scale Electronic Structure Theory

    E-Print Network [OSTI]

    Hoshi, Takeo

    Linear Algebraic Calculation of Green's function for Large-Scale Electronic Structure Theory R (Dated: March 2, 2006) A linear algebraic method named the shifted conjugate-orthogonal-conjugate-gradient method is introduced for large-scale electronic structure calculation. The method gives an iterative

  7. Freezing of 4 He and its liquid-solid interface from density functional theory

    E-Print Network [OSTI]

    Caupin, Frédéric

    Freezing of 4 He and its liquid-solid interface from density functional theory F. Ancilotto,1 M of the method that accurately describes the solid phase and the freezing transition of liquid 4 He at zero phenomenon of crystallization waves, i.e., melting-freezing waves which can easily propagate on the liquid

  8. 2-Loop Functional Renormalization Group Theory of the Depinning Transition Pierre Le Doussal1

    E-Print Network [OSTI]

    Wiese, Kay Jörg

    simulations. The high value of 0.5 found in experiments both on the contact line depinning of liquid Helium2-Loop Functional Renormalization Group Theory of the Depinning Transition Pierre Le Doussal1 , Kay and elastic periodic systems at zero temperature, taking properly into account the non- analytic form

  9. Two-loop functional renormalization group theory of the depinning transition Pierre Le Doussal,1

    E-Print Network [OSTI]

    Wiese, Kay Jörg

    with simulations. The high value of 0.5 in experiments both on Helium contact line depinning and on slow crackTwo-loop functional renormalization group theory of the depinning transition Pierre Le Doussal,1 at zero temperature, taking properly into account the nonanalytic form of the dynamical action. This cures

  10. A Density Functional Theory Study of Hydrogen Adsorption in MOF-5 Tim Mueller and Gerbrand Ceder*

    E-Print Network [OSTI]

    Ceder, Gerbrand

    . The effect of the framework on the physical structure and electronic structure of the organic linker initio molecular dynamics in the generalized gradient approximation to density functional theory, and calculations indicate that the sites with the strongest interaction with hydrogen are located near the Zn4O

  11. Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

    E-Print Network [OSTI]

    Titov, Anatoly

    Relativistic density functional theory modeling of plutonium and americium higher oxide molecules of plutonium and americium higher oxide molecules Andréi Zaitsevskii,1,2,a) Nikolai S. Mosyagin,2,3 Anatoly V of plutonium and americium higher oxide molecules (actinide oxidation states VI through VIII) by two

  12. The Rise of Solitons in Sine-Gordon Field Theory: From Jacobi Amplitude to Gudermannian Function

    E-Print Network [OSTI]

    Leonardo Mondaini

    2014-11-20

    We show how the famous soliton solution of the classical sine-Gordon field theory in $(1+1)$-dimensions may be obtained as a particular case of a solution expressed in terms of the Jacobi amplitude, which is the inverse function of the incomplete elliptic integral of the first kind.

  13. Electronvibration coupling in time-dependent density-functional theory: Application to benzene

    E-Print Network [OSTI]

    Bertsch George F.

    Electron­vibration coupling in time-dependent density-functional theory: Application to benzene G for electron­vibration coupling, we apply it to the optical properties of the ­ * transitions in benzene with the electronic excitations. In this work, we have chosen the benzene model for an exploratory study

  14. Synthesis, crystal structure and DFT studies of N-(4-acetyl-5,5-dimethyl-4,5-dihydro-1,3,4-thiadiazol-2-yl)acetamide

    SciTech Connect (OSTI)

    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.

  15. The importance of nonlinear fluid response in joint density-functional theory studies of battery systems

    E-Print Network [OSTI]

    Gunceler, Deniz; Sundararaman, Ravishankar; Schwarz, Kathleen A; Arias, T A

    2013-01-01

    Delivering the full benefits of first principles calculations to battery materials demands the development of accurate and computationally-efficient electronic structure methods that incorporate the effects of the electrolyte environment and electrode potential. Realistic electrochemical interfaces containing polar surfaces are beyond the regime of validity of existing continuum solvation theories developed for molecules, due to the presence of significantly stronger electric fields. We present an ab initio theory of the nonlinear dielectric and ionic response of solvent environments within the framework of joint density-functional theory, with precisely the same optimizable parameters as conventional polarizable continuum models. We demonstrate that the resulting nonlinear theory agrees with the standard linear models for organic molecules and metallic surfaces under typical operating conditions. However, we find that the saturation effects in the rotational response of polar solvent molecules, inherent to o...

  16. Correlation functions of the energy-momentum tensor in SU(2) gauge theory at finite temperature

    E-Print Network [OSTI]

    Huebner, K; Pica, C

    2008-01-01

    We calculate correlation functions of the energy-momentum tensor in the vicinity of the deconfinement phase transition of (3+1)-dimensional SU(2) gauge theory and discuss their critical behavior in the vicinity of the second order deconfinement transition. We show that correlation functions of the trace of the energy momentum tensor diverge uniformly at the critical point in proportion to the specific heat singularity. Correlation functions of the pressure, on the other hand, stay finite at the critical point. We discuss the consequences of these findings for the analysis of transport coefficients, in particular the bulk viscosity, in the vicinity of a second order phase transition point.

  17. Ultra-nonlocality in density functional theory for photo-emission spectroscopy

    SciTech Connect (OSTI)

    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.

  18. Hybrid Zinc Phthalocyanine/Zinc Oxide System for Photovoltaic De-vices: a DFT and TDDFPT Theoretical Investigation

    E-Print Network [OSTI]

    Giannozzi, Paolo

    Hybrid Zinc Phthalocyanine/Zinc Oxide System for Photovoltaic De- vices: a DFT and TDDFPT in the functioning of hybrid photovoltaic devices. The molecule-surface interactions are also characterized-inorganic photovoltaic devices (OPV and HPV, respectively) have received enormous re- search attention in the last years

  19. Ni(NiO)/single-walled carbon nanotubes composite: Synthesis of electro-deposition, gas sensing property for NO gas and density functional theory calculation

    SciTech Connect (OSTI)

    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), UV–vis–NIR 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 N–Ni interaction as well as the proposition of electron transfer mechanisms from SWCNTs to NO via the Ni medium.

  20. Structure and energetics of solvated ferrous and ferric ions: Car-Parrinello molecular dynamics in the DFT+U formalism

    E-Print Network [OSTI]

    P. H. -L. Sit; Matteo Cococcioni; Nicola Marzari

    2007-01-12

    We implemented a rotationally-invariant Hubbard U extension to density-functional theory in the Car-Parrinello molecular dynamics framework, with the goal of bringing the accuracy of the DFT+U approach to finite-temperature simulations, especially for liquids or solids containing transition-metal ions. First, we studied the effects on the Hubbard U on the static equilibrium structure of the hexa-aqua ferrous and ferric ions, and the inner-sphere reorganization energy for the electron-transfer reaction between aqueous ferrous and ferric ions. It is found that the reorganization energy is increased, mostly as a result of the Fe-O distance elongation in the hexa-aqua ferrous ion. Second, we performed a first-principles molecular dynamics study of the solvation structure of the two aqueous ferrous and ferric ions. The Hubbard term is found to change the Fe-O radial distribution function for the ferrous ion, while having a negligible effect on the aqueous ferric ion. Moreover, the frequencies of vibrations between Fe and oxygen atoms in the first-solvation shell are shown to be unaffected by the Hubbard corrections for both ferrous and ferric ions.

  1. Ferromagnetism in Mn Substituted Zirconia: A Density-functional Theory Study

    E-Print Network [OSTI]

    Xingtao Jia; Wei Yang; Minghui Qin; Xinglai Zhang; Mingai Sun; Jianping Li

    2008-09-05

    We study the electronic structure and magnetism of 25% Mn substituted cubic Zirconia (ZrO2) with several homogeneous and heterogeneous doping profiles using density-functional theory calculations. We find that all doping profiles show half-metallic ferromagnetism (HMF), and delta-doping is most energy favorable while homogeneous doping has largest ferromagnetic stabilization energy. Using crystal field theory, we discuss the formation scheme of HMF. Finally, we speculate the potential spintronics applications for Mn doped ZrO2, especially as spin direction controllment.

  2. Using DFT Methods to Study Activators in Optical Materials Du...

    Office of Scientific and Technical Information (OSTI)

    Using DFT Methods to Study Activators in Optical Materials Du, Mao-Hua ORNL Oak Ridge National Laboratory (ORNL) ORNL work for others; SC USDOE - Office of Science (SC) United...

  3. Degenerate ground states and nonunique potentials: Breakdown and restoration of density functionals

    SciTech Connect (OSTI)

    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.

  4. Dynamical density functional theory for the diffusion of injected Brownian particles

    E-Print Network [OSTI]

    H. Löwen; M. Heinen

    2014-09-08

    While the theory of diffusion of a single Brownian particle in confined geometries is well-established by now, we discuss here the theoretical framework necessary to generalize the theory of diffusion to dense suspensions of strongly interacting Brownian particles. Dynamical density functional theory (DDFT) for classical Brownian particles represents an ideal tool for this purpose. After outlining the basic ingredients to DDFT we show that it can be readily applied to flowing suspensions with time-dependent particle sources. Particle interactions lead to considerable layering in the mean density profiles, a feature that is absent in the trivial case of noninteracting, freely diffusing particles. If the particle injection rate varies periodically in time with a suitable frequency, a resonance in the layering of the mean particle density profile is predicted.

  5. The three-loop beta function in SU(N) lattice gauge theories

    E-Print Network [OSTI]

    B. Alles; A. Feo; H. Panagopoulos

    1996-09-11

    We calculate the third coefficient of the lattice $\\beta$ function in pure Yang-Mills theory. We make use of a computer code for solving perturbation theory analytically on the lattice. We compute the divergent integrals by using a method based on a Taylor expansion of the integrand in powers of the external momenta in $4 - \\epsilon$ dimensions. Our results are in agreement with a previous calculation by M. L\\"uscher and P. Weisz where the authors used a different technique. We also show how this new coefficient modifies the scaling function on the lattice in both the standard and energy schemes. In particular we show that asymptotic scaling is extremely well achieved in the energy scheme.

  6. Double-hybrid density-functional theory with meta-generalized-gradient approximations

    SciTech Connect (OSTI)

    Souvi, Sidi M. O. Sharkas, Kamal; Toulouse, Julien; CNRS, UMR 7616, Laboratoire de Chimie Théorique, 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 Møller-Plesset calculations.

  7. A density functional theory study of electric potential saturation: planar geometry

    E-Print Network [OSTI]

    Gabriel Tellez; Emmanuel Trizac

    2003-08-01

    We investigate the possibility of electrostatic potential saturation, which may lead to the phenomenon of effective charge saturation. The system under study is a uniformly charged infinite plane immersed in an arbitrary electrolyte made up of several micro-species. To describe the electric double layer, we use a generic density functional theory in which the local micro-ionic density profiles are arbitrary functions of the local electrostatic potential. A necessary and sufficient condition is obtained for saturation, whereby the electrostatic potential created by the plane becomes independent of its bare charge, provided the latter is large enough.

  8. Freezing of soft spheres: A critical test for weighted-density-functional theories

    E-Print Network [OSTI]

    Laird, Brian Bostian; Kroll, D. M.

    1990-10-15

    ~ d e ry, r2, & p r2 —p, 0 4814 BRIAN B. LAIRD AND D. M. KROLL 42 Since C is, for the most part, unknown, we approxi- mate it by an as yet unspecified homogeneous two-point function g: C(ri, r2; [p]) = g(~ ri —rz ~; p) . (25) This approximation is due..., NUMBER 8 15 OCTOBER 1990 Freezing of soft spheres: A critical test for weighted-density-functional theories Brian B. Laird and D.M. Kroll Institut fur Festkorperforschung, Forschungszentrurn Julich G rn .b H. .., Postfach I9IS, D SI7-0 Jiilich I, Federal...

  9. Linear-response calculation in the time-dependent density functional theory

    E-Print Network [OSTI]

    Takashi Nakatsukasa; Tsunenori Inakura; Paolo Avogadro; Shuichiro Ebata; Koichi Sato; Kazuhiro Yabana

    2012-09-22

    Linear response calculations based on the time-dependent density-functional theory are presented. Especially, we report results of the finite amplitude method which we have recently proposed as an alternative and feasible approach to the (quasiparticle-)random-phase approximation. Calculated properties of the giant resonances and low-energy E1 modes are discussed. We found a universal linear correlation between the low-energy E1 strength and the neutron skin thickness.

  10. Density functional theory of freezing for soft interactions in two dimensions

    E-Print Network [OSTI]

    Sven van Teeffelen; Christos N. Likos; Norman Hoffmann; Hartmut Löwen

    2006-04-18

    A density functional theory of two-dimensional freezing is presented for a soft interaction potential that scales as inverse cube of particle distance. This repulsive potential between parallel, induced dipoles is realized for paramagnetic colloids on an interface, which are additionally exposed to an external magnetic field. An extended modified weighted density approximation which includes correct triplet correlations in the liquid state is used. The theoretical prediction of the freezing transition is in good agreement with experimental and simulation data.

  11. Nuclear charge-exchange excitations in localized covariant density functional theory

    E-Print Network [OSTI]

    H. Z. Liang; J. Meng; T. Nakatsukasa; Z. M. Niu; P. Ring; X. Roca-Maza; N. Van Giai; P. W. Zhao

    2013-10-15

    The recent progress in the studies of nuclear charge-exchange excitations with localized covariant density functional theory is briefly presented, by taking the fine structure of spin-dipole excitations in 16O as an example. It is shown that the constraints introduced by the Fock terms of the relativistic Hartree-Fock scheme into the particle-hole residual interactions are straightforward and robust.

  12. Steam Reforming on Transition-metal Carbides from Density-functional Theory

    SciTech Connect (OSTI)

    Vojvodic, Aleksandra

    2012-05-11

    A screening study of the steam reforming reaction on clean and oxygen covered early transition-metal carbides surfaces is performed by means of density-functional theory calculations. It is found that carbides provide a wide spectrum of reactivities, from too reactive via suitable to too inert. Several molybdenum-based systems are identified as possible steam reforming catalysts. The findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.

  13. Covariant density functional theory with two-phonon coupling in nuclei

    SciTech Connect (OSTI)

    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.

  14. Assessment of Density Functional Methods for Exciton Binding Energies and Related Optoelectronic Properties

    E-Print Network [OSTI]

    Lee, Jui-Che; Lin, Shiang-Tai

    2015-01-01

    The exciton binding energy, the energy required to dissociate an excited electron-hole pair into free charge carriers, is one of the key factors to the optoelectronic performance of organic materials. However, it remains unclear whether modern quantum-mechanical calculations, mostly based on Kohn-Sham density functional theory (KS-DFT) and time-dependent density functional theory (TDDFT), are reliably accurate for exciton binding energies. In this study, the exciton binding energies and related optoelectronic properties (e.g., the ionization potentials, electron affinities, fundamental gaps, and optical gaps) of 121 small- to medium-sized molecules are calculated using KS-DFT and TDDFT with various density functionals. Our KS-DFT and TDDFT results are compared with those calculated using highly accurate CCSD and EOM-CCSD methods, respectively. The omegaB97, omegaB97X, and omegaB97X-D functionals are shown to generally outperform (with a mean absolute error of 0.36 eV) other functionals for the properties inve...

  15. Assessment of Density Functional Methods for Exciton Binding Energies and Related Optoelectronic Properties

    E-Print Network [OSTI]

    Jui-Che Lee; Jeng-Da Chai; Shiang-Tai Lin

    2015-08-29

    The exciton binding energy, the energy required to dissociate an excited electron-hole pair into free charge carriers, is one of the key factors to the optoelectronic performance of organic materials. However, it remains unclear whether modern quantum-mechanical calculations, mostly based on Kohn-Sham density functional theory (KS-DFT) and time-dependent density functional theory (TDDFT), are reliably accurate for exciton binding energies. In this study, the exciton binding energies and related optoelectronic properties (e.g., the ionization potentials, electron affinities, fundamental gaps, and optical gaps) of 121 small- to medium-sized molecules are calculated using KS-DFT and TDDFT with various density functionals. Our KS-DFT and TDDFT results are compared with those calculated using highly accurate CCSD and EOM-CCSD methods, respectively. The omegaB97, omegaB97X, and omegaB97X-D functionals are shown to generally outperform (with a mean absolute error of 0.36 eV) other functionals for the properties investigated.

  16. Linear response theory and neutrino mean free path using Brussels-Montreal Skyrme functionals

    E-Print Network [OSTI]

    A. Pastore; M. Martini; D. Davesne; J. Navarro; S. Goriely; N. Chamel

    2014-08-12

    The Brussels-Montreal Skyrme functionals have been successful to describe properties of both finite nuclei and infinite homogeneous nuclear matter. In their latest version, these functionals have been equipped with two extra density-dependent terms in order to reproduce simultaneously ground state properties of nuclei and infinite nuclear matter properties while avoiding at the same time the arising of ferromagnetic instabilities. In the present article, we extend our previous results of the linear response theory to include such extra terms at both zero and finite temperature in pure neutron matter. The resulting formalism is then applied to derive the neutrino mean free path. The predictions from the Brussels-Montreal Skyrme functionals are compared with ab-initio methods.

  17. Time-dependent density functional theory quantum transport simulation in non-orthogonal basis

    SciTech Connect (OSTI)

    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.

  18. Analytic cubic and quartic force fields using density-functional theory

    SciTech Connect (OSTI)

    Ringholm, Magnus; Gao, Bin; Thorvaldsen, Andreas J.; Ruud, Kenneth; Jonsson, Dan; High Performance Computing Group, University of Tromsø—The Arctic University of Norway, 9037 Tromsø ; Bast, Radovan; Ekström, Ulf; Helgaker, Trygve

    2014-01-21

    We present the first analytic implementation of cubic and quartic force constants at the level of Kohn–Sham 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 exchange–correlation kernels. We use generalized second-order vibrational perturbation theory to calculate the fundamental frequencies of methane, ethane, benzene, and aniline, comparing B3LYP, BLYP, and Hartree–Fock results. The Hartree–Fock 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.

  19. Correlation of Theory and Function in Well-Defined Bimetallic Electrocatalysts - Final Report

    SciTech Connect (OSTI)

    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.

  20. Alternative separation of exchange and correlation energies in range-separated density-functional perturbation theory

    E-Print Network [OSTI]

    Cornaton, Yann; Jensen, Hans Jørgen Aa; Fromager, Emmanuel

    2013-01-01

    An alternative separation of short-range exchange and correlation energies is used in the framework of second-order range-separated density-functional perturbation theory. This alternative separation was initially proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] and relies on a long-range interacting wavefunction instead of the non-interacting Kohn-Sham one. When second-order corrections to the density are neglected, the energy expression reduces to a range-separated double-hybrid (RSDH) type of functional, RSDHf, where "f" stands for "full-range integrals" as the regular full-range interaction appears explicitly in the energy expression when expanded in perturbation theory. In contrast to usual RSDH functionals, RSDHf describes the coupling between long- and short-range correlations as an orbital-dependent contribution. Calculations on the first four noble-gas dimers show that this coupling has a significant effect on the potential energy curves in the equilibrium region, improving the accurac...

  1. 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(?), Cu10Zr7(?), 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(?). 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

  2. Free-energy functional of the electronic potential for Schrödinger-Poisson theory

    E-Print Network [OSTI]

    Vikram Jadhao; Kaushik Mitra; Francisco J. Solis; Monica Olvera de la Cruz

    2014-12-15

    In the study of model electronic device systems where electrons are typically under confinement, a key obstacle is the need to iteratively solve the coupled Schr\\"{o}dinger-Poisson (SP) equation. It is possible to bypass this obstacle by adopting a variational approach and obtaining the solution of the SP equation by minimizing a functional. Further, using molecular dynamics methods that treat the electronic potential as a dynamical variable, the functional can be minimized on the fly in conjunction with the update of other dynamical degrees of freedom leading to considerable reduction in computational costs. But such approaches require access to a true free-energy functional, one that evaluates to the equilibrium free energy at its minimum. In this paper, we present a variational formulation of the Schr\\"{o}dinger-Poisson (SP) theory with the needed free-energy functional of the electronic potential. We apply our formulation to semiconducting nanostructures and provide the expression of the free-energy functional for narrow channel quantum wells where the local density approximation yields accurate physics and for the case of wider channels where Thomas-Fermi approximation is valid.

  3. Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory

    SciTech Connect (OSTI)

    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(?), Cu10Zr7(?), 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, namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu10Zr7(?). 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.

  4. Growth mechanism of atomic layer deposition of zinc oxide: A density functional theory approach

    SciTech Connect (OSTI)

    Afshar, Amir; Cadien, Kenneth C., E-mail: kcadien@ualberta.ca [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4 (Canada)

    2013-12-16

    Atomic layer deposition of zinc oxide (ZnO) using diethylzinc (DEZ) and water is studied using density functional theory. The reaction pathways between the precursors and ZnO surface sites are discussed. Both reactions proceed by the formation of intermediate complexes on the surface. The Gibbs free energy of the formation of these complexes is positive at temperatures above ?120?°C and ?200?°C for DEZ and water half-reactions, respectively. Spectroscopic ellipsometry results show that the growth per cycle changes at approximately the same temperatures.

  5. DFT+U Study of CeO2 and Its Native Defects

    E-Print Network [OSTI]

    Huang, Bolong; Gillen, Roland; Robertson, John

    2014-10-14

    , Frenkel defect, pseudopotential transferability, oxidation catalyst 1. Introduction CeO2 is an important lanthanide oxide which is widely used as an oxygen buffer in car exhaust catalysts1, as a fast ion conductor in solid state fuel cells2, as a... as optimization of pseudopotentials47. The PBE functional was chosen for PBE+U calculations with a kinetic cutoff energy of 750eV, which expands the valence electrons states in a plane-wave basis set. The ensemble DFT (EDFT) method of Marzari et al48 is used...

  6. Electronic and structural properties of ultrathin tungsten nanowires and nanotubes by density functional theory calculation

    SciTech Connect (OSTI)

    Sun, Shih-Jye [Department of Applied Physics, National University of Kaohsiung, Kaohsiung 811, Taiwan (China); Lin, Ken-Huang; Li, Jia-Yun [Department of Mechanical and Electro-Mechanical Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Ju, Shin-Pon, E-mail: jushin-pon@mail.nsysu.edu.tw [Department of Mechanical and Electro-Mechanical Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan (China)

    2014-10-07

    The simulated annealing basin-hopping method incorporating the penalty function was used to predict the lowest-energy structures for ultrathin tungsten nanowires and nanotubes of different sizes. These predicted structures indicate that tungsten one-dimensional structures at this small scale do not possess B.C.C. configuration as in bulk tungsten material. In order to analyze the relationship between multi-shell geometries and electronic transfer, the electronic and structural properties of tungsten wires and tubes including partial density of state and band structures which were determined and analyzed by quantum chemistry calculations. In addition, in order to understand the application feasibility of these nanowires and tubes on nano-devices such as field emitters or chemical catalysts, the electronic stability of these ultrathin tungsten nanowires was also investigated by density functional theory calculations.

  7. Orbital-free density functional theory of out-of-plane charge screening in graphene

    E-Print Network [OSTI]

    Jianfeng Lu; Vitaly Moroz; Cyrill B. Muratov

    2015-06-30

    We propose a density functional theory of Thomas-Fermi-Dirac-von Weizs\\"acker type to describe the response of a single layer of graphene resting on a dielectric substrate to a point charge or a collection of charges some distance away from the layer. We formulate a variational setting in which the proposed energy functional admits minimizers, both in the case of free graphene layers and under back-gating. We further provide conditions under which those minimizers are unique and correspond to configurations consisting of inhomogeneous density profiles of charge carrier of only one type. The associated Euler-Lagrange equation for the charge density is also obtained, and uniqueness, regularity and decay of the minimizers are proved under general conditions. In addition, a bifurcation from zero to non-zero response at a finite threshold value of the external charge is proved.

  8. Quasi-particle energy spectra in local reduced density matrix functional theory

    SciTech Connect (OSTI)

    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.

  9. Building A Universal Nuclear Energy Density Functional (UNEDF)

    SciTech Connect (OSTI)

    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.

  10. Flow of colloidal solids and fluids through constrictions: dynamical density functional theory versus simulation

    E-Print Network [OSTI]

    Urs Zimmermann; Frank Smallenburg; Hartmut Löwen

    2015-12-02

    Using both dynamical density functional theory and particle-resolved Brownian dynamics simulations, we explore the flow of two-dimensional colloidal solids and fluids driven through a linear channel with a geometric constriction. The flow is generated by a constant external force acting on all colloids. The initial configuration is equilibrated in the absence of flow and then the external force is switched on instantaneously. Upon starting the flow, we observe four different scenarios: a complete blockade, a monotonic decay to a constant particle flux (typical for a fluid), a damped oscillatory behaviour in the particle flux, and a long-lived stop-and-go behaviour in the flow (typical for a solid). The dynamical density functional theory describes all four situations but predicts infinitely long undamped oscillations in the flow which are always damped in the simulations. We attribute the mechanisms of the underlying stop-and-go flow to symmetry conditions on the flowing solid. Our predictions are verifiable in real-space experiments on magnetic colloidal monolayers which are driven through structured microchannels and can be exploited to steer the flow throughput in microfluidics.

  11. Uncertainty Quantification for Nuclear Density Functional Theory and Information Content of New Measurements

    E-Print Network [OSTI]

    J. D. McDonnell; N. Schunck; D. Higdon; J. Sarich; S. M. Wild; W. Nazarewicz

    2015-01-15

    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. 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.

  12. On a Gopakumar-Vafa form of partition function of Chern-Simons theory on classical and exceptional lines

    E-Print Network [OSTI]

    R. L. Mkrtchyan

    2014-10-29

    We show that partition function of Chern-Simons theory on three-sphere with classical and exceptional groups (actually on the whole corresponding lines in Vogel's plane) can be represented as ratio of respectively triple and double sine functions (last function is essentially a modular quantum dilogarithm). The product representation of sine functions gives Gopakumar-Vafa structure form of partition function, which in turn gives a corresponding integer invariants of manifold after geometrical transition. In this way we suggest to extend gauge/string duality to exceptional groups, although one still have to resolve few problems. In both classical and exceptional cases an additional terms, non-perturbative w.r.t. the string coupling constant, appear. The full universal partition function of Chern-Simons theory on three-sphere is shown to be the ratio of quadruple sine functions. We also briefly discuss the matrix model for exceptional line.

  13. Describing excited state relaxation and localization in TiO2 nanoparticles using TD-DFT

    SciTech Connect (OSTI)

    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 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 TiO2 nanoparticles is predicted to be associated with a large Stokes’ shift.

  14. Complex-energy approach to sum rules within nuclear density functional theory

    E-Print Network [OSTI]

    Nobuo Hinohara; Markus Kortelainen; Witold Nazarewicz; Erik Olsen

    2015-01-28

    The linear response of the nucleus to an external field contains unique information about the effective interaction, correlations, 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 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 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 FAM based on the QRPA. To compute sum rules, we carry out contour integration of the response function in the complex-energy plane. We benchmark our results against the conventional matrix formulation of the QRPA theory, the Thouless theorem for the energy-weighted sum rule, and the dielectric theorem for the inverse energy-weighted sum rule. We demonstrate that calculated sum-rule values agree with those obtained from the matrix formulation of the QRPA. We also discuss the applicability of both the Thouless theorem about the energy-weighted sum rule and the dielectric theorem for the inverse energy-weighted sum rule to nuclear density functional theory in cases when the EDF is not based on a Hamiltonian. 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. The FAM formulation is especially useful when standard theorems based on commutation relations involving the nuclear Hamiltonian and external field cannot be used.

  15. Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy And Time Dependent-Density Functional Theory

    SciTech Connect (OSTI)

    Kozimor, S.A.; Yang, P.; Batista, E.R.; Boland, K.S.; Burns, C.J.; Christensen, C.N.; Clark, D.L.; Conradson, S.D.; Hay, P.J.; Lezama, J.S.; Martin, R.L.; Schwarz, D.E.; Wilkerson, M.P.; Wolfsberg, L.E.

    2009-05-20

    For 3-5d transition-metal ions, the (C{sub 5}R{sub 5}){sub 2}MCl{sub 2} (R = H, Me for M = Ti, Zr, Hf) bent metallocenes represent a series of compounds that have been central in the development of organometallic chemistry and homogeneous catalysis. Here, we evaluate how changes in the principal quantum number for the group IV (C{sub 5}H{sub 5}){sub 2}MCl{sub 2} (M = Ti, Zr, Hf; 1-3, respectively) complexes affects the covalency of M-Cl bonds through application of Cl K-edge X-ray Absorption Spectroscopy (XAS). Spectra were recorded on solid samples dispersed as a thin film and encapsulated in polystyrene matrices to reliably minimize problems associated with X-ray self-absorption. The data show that XAS pre-edge intensities can be quantitatively reproduced when analytes are encapsulated in polystyrene. Cl K-edge XAS data show that covalency in M-Cl bonding changes in the order Ti > Zr > Hf and demonstrates that covalency slightly decreases with increasing principal quantum number in 1-3. The percent Cl 3p character was experimentally determined to be 26, 23, and 18% per M-Cl bond in the thin-film samples for 1-3 respectively and was indistinguishable from the polystyrene samples, which analyzed as 25, 25, and 19% for 1-3, respectively. To aid in interpretation of Cl K-edge XAS, 1-3 were also analyzed by ground-state and time-dependent density functional theory (TD-DFT) calculations. The calculated spectra and percent chlorine character are in close agreement with the experimental observations, and show 20, 18, and 17% Cl 3p character per M-Cl bond for 1-3, respectively. Polystyrene matrix encapsulation affords a convenient method to safely contain radioactive samples to extend our studies to include actinide elements, where both 5f and 6d orbitals are expected to play a role in M-Cl bonding and where transition assignments must rely on accurate theoretical calculations.

  16. Coupled cluster benchmarks of water monomers and dimers extracted from density-functional theory liquid water: The importance of monomer

    E-Print Network [OSTI]

    Alavi, Ali

    Coupled cluster benchmarks of water monomers and dimers extracted from density-functional theory functionals in simulations of liquid water, water monomers and dimers were extracted from a PBE simulation liquid water: The importance of monomer deformations Biswajit Santra,1 Angelos Michaelides,1,2,a

  17. Spin Contamination in Hartree-Fock and Density Functional Theory Wavefunctions in Modeling of Adsorption on Graphite

    E-Print Network [OSTI]

    Truong, Thanh N.

    Spin Contamination in Hartree-Fock and Density Functional Theory Wavefunctions in Modeling: April 27, 2000 We have examined the effect of spin contamination in single determinant wave function) method, we found that UHF has a large spin contamination. Consequently, this yields large errors

  18. Million Atom KS-DFT with CP2K 

    E-Print Network [OSTI]

    Bethune, Iain; Carter, Adam; Guo, Xu; Korosoglou, Paschalis

    2011-01-01

    CP2K is a powerful materials science and computational chemistry code and is widely used by research groups across Europe and beyond. The recent addition of a linear scaling KS-DFT method within the code has made it possible to simulate systems...

  19. Enantioselectivity of (321) chiral noble metal surfaces: A density functional theory study of lactate adsorption

    SciTech Connect (OSTI)

    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)

  20. Fundamental gaps with approximate density functionals: The derivative discontinuity revealed from ensemble considerations

    SciTech Connect (OSTI)

    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.

  1. Full Fermion-Boson Vertex Function Derived in terms of the Ward-Takahashi Relations in Abelian Gauge Theory

    E-Print Network [OSTI]

    Han-xin He

    2006-06-06

    I present an approach to derive the full fermion-boson vertex function in four-dimensional Abelian gauge theory in terms of a set of normal (longitudinal) and transverse Ward-Takahashi relations for the fermion-boson and axial-vector vertices in momentum space in the case of massless fermion. Such a derived fermion-boson vertex function should be satisfied both perturbatively and non-perturbatively. I show that, by an explicit computation, such a derived full fermion-boson vertex function to one-loop order leads to the same result as one obtained in perturbation theory.

  2. Real-time linear response for time-dependent density-functional theory Department of Physical Chemistry and the Lise Meitner Minerva-Center for Quantum Chemistry,

    E-Print Network [OSTI]

    Baer, Roi

    Real-time linear response for time-dependent density-functional theory Roi Baer Department a linear-response approach for time-dependent density-functional theories using time-adiabatic functionals describing the evolution is not strictly linear in the wave function representation. Only after going

  3. Coherent control and time-dependent density functional theory: Towards creation of wave packets by ultrashort laser pulses

    SciTech Connect (OSTI)

    Raghunathan, Shampa; Nest, Mathias [Theoretische Chemie, TU Muenchen, Lichtenbergstr. 4, 85747 Garching (Germany)

    2012-02-14

    Explicitly time-dependent density functional theory (TDDFT) is a formally exact theory, which can treat very large systems. However, in practice it is used almost exclusively in the adiabatic approximation and with standard ground state functionals. Therefore, if combined with coherent control theory, it is not clear which control tasks can be achieved reliably, and how this depends on the functionals. In this paper, we continue earlier work in order to establish rules that answer these questions. Specifically, we look at the creation of wave packets by ultrashort laser pulses that contain several excited states. We find that (i) adiabatic TDDFT only works if the system is not driven too far from the ground state, (ii) the permanent dipole moments involved should not differ too much, and (iii) these results are independent of the functional used. Additionally, we find an artifact that produces fluence-dependent excitation energies.

  4. Linear response theory in asymmetric nuclear matter for Skyrme functionals including spin-orbit and tensor terms

    E-Print Network [OSTI]

    D. Davesne; A. Pastore; J. Navarro

    2014-02-18

    The formalism of linear response theory for a Skyrme functional including spin-orbit and tensor terms is generalized to the case of infinite nuclear matter with arbitrary isospin asymmetry. Response functions are obtained by solving an algebraic system of equations, which is explicitly given. Spin-isospin strength functions are analyzed varying the conditions of density, momentum transfer, asymmetry and temperature. The presence of instabilities, including the spinodal one, is studied by means of the static susceptibility.

  5. Density functional theory (DFT) and ab initio molecular orbital calculations have been employed to determine the structures and energies of the isomers of the OH-toluene adduct, the methyl hydroxycyclohexadienyl radical, and their corresponding transitio

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantityBonneville Power Administration would like submit theCovalent Bonding Low-Cost2DepartmentDelta Dental

  6. Theoretical Insight into the Interactions of TMA-Benzene and TMA-Pyrrole with B3LYP Density-Functional Theory (DFT) and ab Initio Second Order Mller-Plesset Perturbation

    E-Print Network [OSTI]

    Sussman, Joel L.

    Theoretical Insight into the Interactions of TMA-Benzene and TMA-Pyrrole with B3LYP Density theoretical investigation of the tetramethylammonium(TMA)-benzene and TMA-pyrrole complexes has been performed density in the 5 6 aromatic system of pyrrole is larger than that in the 6 6 system of benzene

  7. The Komar mass function in the de-Rham-Gabadadze-Tolley non-linear theory of massive gravity

    E-Print Network [OSTI]

    Ivan Arraut

    2014-12-10

    I derive the Komar mass/function for the Schwarszchild de-Sitter (S-dS) black-hole inside the dRGT non-linear theory of massive gravity by taking the usual notion of time-like Killing vector in unitary gauge. The dRGT Komar function depends on the dynamics of the St\\"uckelberg fields through the gauge transformation function. It goes to the standard value obtained in General Relativity (GR) if the spatial derivative of the gauge function vanishes. In such a case, the (gauge) function corresponds to the usual notion of time as in GR.

  8. First principles DFT study of ferromagnetism in SnO{sub 2} induced by doped group 1A and 2A non-magnetic elements X (X=Li, Na, K, Be, Mg, Ca)

    SciTech Connect (OSTI)

    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.

  9. Time-odd mean fields in covariant density functional theory I. Non-rotating systems

    E-Print Network [OSTI]

    A. V. Afanasjev; H. Abusara

    2010-10-09

    Time-odd mean fields (nuclear magnetism) are analyzed in the framework of covariant density functional theory (CDFT). It is shown that they always provide additional binding to the binding energies of odd-mass nuclei. This additional binding only weakly depends on the RMF parametrization reflecting good localization of the properties of time-odd mean fields in CDFT. The underlying microscopic mechanism is discussed in detail. Time-odd mean fields affect odd-even mass differences. However, our analysis suggests that the modifications of the strength of pairing correlations required to compensate for their effects are modest. In contrast, time-odd mean fields have profound effect on the properties of odd-proton nuclei in the vicinity of proton-drip line. Their presence can modify the half-lives of proton-emitters (by many orders of magnitude in light nuclei) and affect considerably the possibilities of their experimental observation.

  10. Green's function method for single-particle resonant states in relativistic mean field theory

    E-Print Network [OSTI]

    T. T. Sun; S. Q. Zhang; Y. Zhang; J. N. Hu; J. Meng

    2014-09-30

    Relativistic mean field theory is formulated with the Green's function method in coordinate space to investigate the single-particle bound states and resonant states on the same footing. Taking the density of states for free particle as a reference, the energies and widths of single-particle resonant states are extracted from the density of states without any ambiguity. As an example, the energies and widths for single-neutron resonant states in $^{120}$Sn are compared with those obtained by the scattering phase-shift method, the analytic continuation in the coupling constant approach, the real stabilization method and the complex scaling method. Excellent agreements are found for the energies and widths of single-neutron resonant states.

  11. Quantitative assessment of electrostatic embedding in Density Functional Theory calculations of biomolecular systems

    SciTech Connect (OSTI)

    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.

  12. Nuclear matrix elements in neutrinoless double beta decay: beyond mean-field covariant density functional theory

    E-Print Network [OSTI]

    Yao, J M; Hagino, K; Ring, P; Meng, J

    2014-01-01

    We report a systematic study of nuclear matrix elements (NMEs) in neutrinoless double-beta decays with state-of-the-art beyond mean-field covariant density functional theory. The dynamic effects of particle-number and angular-momentum conservations as well as quadrupole shape fluctuations are taken into account with projections and generator coordinate method for both initial and final nuclei. The full relativistic transition operator is adopted to calculate the NMEs which are found to be consistent with the results of previous beyond non-relativistic mean-field calculation based on a Gogny force with the exception of $^{150}$Nd. Our study shows that the total NMEs can be well approximated by the pure axial-vector coupling term, the calculation of which is computationally much cheaper than that of full terms.

  13. Green's function multiple-scattering theory with a truncated basis set: An augmented-KKR formalism

    SciTech Connect (OSTI)

    Alam, Aftab [Indian Institute of Technology Bombay; Khan, Suffian N [Ames Laboratory; Smirnov, A V [Ames Laboratory; Nicholson, D M [Oak Ridge National Laboratory; Johnson, Duane D [Ames Laboratory

    2014-11-01

    The Korringa-Kohn-Rostoker (KKR) Green's function, multiple-scattering theory is an efficient site-centered, electronic-structure technique for addressing an assembly of N scatterers. Wave functions are expanded in a spherical-wave basis on each scattering center and indexed up to a maximum orbital and azimuthal number Lmax=(l,m)max, while scattering matrices, which determine spectral properties, are truncated at Ltr=(l,m)tr where phase shifts ?l>ltr are negligible. Historically, Lmax is set equal to Ltr, which is correct for large enough Lmax but not computationally expedient; a better procedure retains higher-order (free-electron and single-site) contributions for Lmax>Ltr with ?l>ltr set to zero [X.-G. Zhang and W. H. Butler, Phys. Rev. B 46, 7433 (1992)]. We present a numerically efficient and accurate augmented-KKR Green's function formalism that solves the KKR equations by exact matrix inversion [R3 process with rank N(ltr+1)2] and includes higher-L contributions via linear algebra [R2 process with rank N(lmax+1)2]. The augmented-KKR approach yields properly normalized wave functions, numerically cheaper basis-set convergence, and a total charge density and electron count that agrees with Lloyd's formula. We apply our formalism to fcc Cu, bcc Fe, and L10 CoPt and present the numerical results for accuracy and for the convergence of the total energies, Fermi energies, and magnetic moments versus Lmax for a given Ltr.

  14. Accurate molecular dynamics and nuclear quantum effects at low cost by multiple steps in real and imaginary time: using density functional theory to accelerate wavefunction methods

    E-Print Network [OSTI]

    Kapil, Venkat; Ceriotti, Michele

    2015-01-01

    The development and implementation of increasingly accurate methods for electronic structure calculations mean that, for many atomistic simulation problems, treating light nuclei as classical particles is now one of the most serious approximations. Even though recent developments have significantly reduced the overhead for modelling the quantum nature of the nuclei, the cost is still prohibitive when combined with advanced electronic structure methods. Here we present how multiple time step integrators can be combined with ring-polymer contraction techniques (effectively, multiple time stepping in imaginary time) to reduce virtually to zero the overhead of modelling nuclear quantum effects, while describing inter-atomic forces at high levels of electronic structure theory. This is demonstrated for a combination of MP2 and semi-local DFT applied to the Zundel cation. The approach can be seamlessly combined with other methods to reduce the computational cost of path integral calculations, such as high-order fac...

  15. Time-dependent density-functional theory for strong-field multiphoton processes: Application to the study of the role of dynamical electron correlation

    E-Print Network [OSTI]

    Chu, Shih-I

    Time-dependent density-functional theory for strong-field multiphoton processes: Application 1997 We present a self-interaction-free time-dependent density-functional theory TDDFT. The theory is based on the extension of the time-dependent Kohn-Sham formalism. The time-dependent exchange

  16. Density functional theory study of the interaction of vinyl radical, ethyne, and ethene with benzene, aimed to define an affordable computational level to investigate stability trends in large van der Waals complexes

    SciTech Connect (OSTI)

    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 ?E{sub AB}. Counterpoise-corrected interaction energies ?E{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, ?B97X-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, ?E{sub CC-MP}, a CCSD(T)/CBS estimate is obtained and taken as a computational energy reference. At DFT, variations in ?E{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 ?(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 ??? associations of different PAHs (R, made by 10, 16, or 24 C atoms) and P (80 C atoms)

  17. Exploring the interaction between lithium ion and defective graphene surface using dispersion corrected DFT studies

    SciTech Connect (OSTI)

    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 ? 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-? 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.

  18. Complex-energy approach to sum rules within nuclear density functional theory

    E-Print Network [OSTI]

    Hinohara, Nobuo; Nazarewicz, Witold; Olsen, Erik

    2015-01-01

    The linear response of the nucleus to an external field contains unique information about the effective interaction, correlations, 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 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 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 FAM based on the QRPA. To compute sum rules, we carry out contour integration of the response function in the complex-energy plane. We benchmark our results against the conventional matrix formulation of the QRPA theory...

  19. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

    SciTech Connect (OSTI)

    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.

  20. Uranium (VI)Bis(imido) chalcogenate complexes:synthesis and density functional theory analysis

    SciTech Connect (OSTI)

    Spencer, Liam P [Los Alamos National Laboratory; Batista, Enrique R [Los Alamos National Laboratory; Boncella, James M [Los Alamos National Laboratory; Yang, Ping [Los Alamos National Laboratory; Scott, Brian L [Los Alamos National Laboratory

    2009-01-01

    Bis(imido) uranium(VI) trans- and cis-dichalcogenate complexes with the general formula U(NtBu)2(EAr)2(OPPh3)2 (EAr = O-2-tBuC6H4, SPh, SePh, TePh) and U(NtBu)2(EAr)2(R2bpy) (EAr = SPh, SePh, TePh) (R2bpy = 4,4'-disubstituted-2,2'-bipyridyl, R = Me, tBu) have been prepared. This family of complexes includes the first reported monodentate selenolate and tellurolate complexes of uranium(VI). Density functional theory calculations show that covalent interactions in the U-E bond increase in the trans-dichalcogenate series U(NtBu)2(EAr)2(OPPh3)2 as the size of the chalcogenate donor increases and that both 5f and 6d orbital participation is important in the M-E bonds of U-S, U-Se, and U-Te complexes.

  1. Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study

    SciTech Connect (OSTI)

    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.

  2. Potential energy surfaces of actinide and transfermium nuclei from multi-dimensional constraint covariant density functional theories

    E-Print Network [OSTI]

    Bing-Nan Lu; Jie Zhao; En-Guang Zhao; Shan-Gui Zhou

    2013-03-04

    Multi-dimensional constrained covariant density functional theories were developed recently. In these theories, all shape degrees of freedom \\beta_{\\lambda\\mu} deformations with even \\mu are allowed, e.g., \\beta_{20}, \\beta_{22}, \\beta_{30}, \\beta_{32}, \\beta_{40}, \\beta_{42}, \\beta_{44}, and so on and the CDFT functional can be one of the following four forms: the meson exchange or point-coupling nucleon interactions combined with the non-linear or density-dependent couplings. In this contribution, some applications of these theories are presented. The potential energy surfaces of actinide nuclei in the (\\beta_{20}, \\beta_{22}, \\beta_{30}) deformation space are investigated. It is found that besides the octupole deformation, the triaxiality also plays an important role upon the second fission barriers. The non-axial reflection-asymmetric \\beta_{32} shape in some transfermium nuclei with N = 150, namely 246Cm, 248Cf, 250Fm, and 252No are studied.

  3. Fourth-order coherence-function theory of laser-induced molecular reorientational grating and population grating

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    2089 Fourth-order coherence-function theory of laser-induced molecular reorientational grating mécanisme de formation du réseau de population. Abstract. 2014 We have employed fourth-order coherence proposed to distinguish molecular reorientational grating from thermal grating. We then apply the fourth

  4. Catalytic Role of Gold in Gold-Based Catalysts: A Density Functional Theory Study on the CO Oxidation on Gold

    E-Print Network [OSTI]

    Alavi, Ali

    Catalytic Role of Gold in Gold-Based Catalysts: A Density Functional Theory Study on the CO Oxidation on Gold Zhi-Pan Liu and P. Hu* Contribution from the School of Chemistry, The Queen's Uni years, being regarded as a new generation of catalysts due to their unusually high catalytic performance

  5. Dynamical mean-field theory using Wannier functions: A flexible route to electronic structure calculations of strongly correlated materials

    E-Print Network [OSTI]

    Boyer, Edmond

    Dynamical mean-field theory using Wannier functions: A flexible route to electronic structure materials with different degrees of structural and electronic complexity, SrVO3 and BaVS3, are investigated calculations of strongly correlated materials F. Lechermann,1,2, * A. Georges,1 A. Poteryaev,1 S. Biermann,1 M

  6. Evaluation of S2 for correlated wave functions and spin projection of unrestricted Mbller-Plesset perturbation theory

    E-Print Network [OSTI]

    Schlegel, H. Bernhard

    Evaluation of S2 for correlated wave functions and spin projection of unrestricted Mbller to evaluate S2 for unrestricted MQller-Plesset perturbation theory (UMPn), coupled clusters (UCCSD), quadratic configuration interaction (UQCISD), and Brueckner doubles (UBD) methods, and to evaluate UMP3 and UMP4 energies

  7. THE JOURNAL OF CHEMICAL PHYSICS 142, 064109 (2015) Analytic derivative couplings in time-dependent density functional theory

    E-Print Network [OSTI]

    Herbert, John

    2015-01-01

    , but can be calculated with only a moderate increase in computational cost beyond what is required to full configuration interaction calculations, suggest that the two approaches perform equally well for many molecular systems, provided that the underlying DFT method affords accurate potential energy

  8. Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

    SciTech Connect (OSTI)

    Piotrowski, Mauricio J.; Piquini, Paulo; Da Silva, Juarez L. F. [Departamento de Fisica, Universidade Federal de Santa Maria, Santa Maria 97105-900, RS (Brazil); Instituto de Fisica de Sao Carlos, Universidade de Sao Paulo, Cx. Postal 369, Sao Carlos 13560-970, SP (Brazil)

    2010-04-15

    The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M{sub 13}. First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first-principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M{sub 13} structures. Several new lower energy configurations were identified, e.g., Pd{sub 13}, W{sub 13}, Pt{sub 13}, etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au{sub 13}, we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

  9. The magnetic and electronic structure of vanadyl pyrophosphate from density functional theory

    SciTech Connect (OSTI)

    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, JOPO = ?156.8 K and JO = ?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, Jlayer = 19.2 K and Jchain = 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 JOPO originates from a super-exchange interaction through the bridging –O–P–O– unit. In contrast, JO results from a direct overlap of 3dx²?y² orbitals on two vanadium atoms in the same V2O8 motif, making it very sensitive to structural fluctuations. Based on the variations in V–O bond length as a function of strain along a, we found that the V–O 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 JO, changing the magnetic structure and spin gap of VOPO. This result also suggests that assuming JO to be a constant over the range of 2–300 K whilst fitting couplings to the experimental magnetic susceptibility is an invalid method. Regarding its role as a catalyst, the bonding pattern suggests that O2 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.

  10. Magnetism in undoped ZnS studied from density functional theory

    SciTech Connect (OSTI)

    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.

  11. Ab initio molecular dynamics with nuclear quantum effects at classical cost: ring polymer contraction for density functional theory

    E-Print Network [OSTI]

    Marsalek, Ondrej

    2015-01-01

    Path integral molecular dynamics simulations, combined with an ab initio evaluation of interactions using electronic structure theory, incorporate the quantum mechanical nature of both the electrons and nuclei, which are essential to accurately describe systems containing light nuclei. However, path integral simulations have traditionally required a computational cost around two orders of magnitude greater than treating the nuclei classically, making them prohibitively costly for most applications. Here we show that the cost of path integral simulations can be dramatically reduced by extending our ring polymer contraction approach to ab initio molecular dynamics simulations. By using density functional tight binding as a reference system, we show that our ab initio ring polymer contraction (AI-RPC) scheme gives rapid and systematic convergence to the full path integral density functional theory result. We demonstrate the efficiency of this approach in ab initio simulations of liquid water and the reactive pro...

  12. Diagnosing Chaos Using Four-Point Functions in Two-Dimensional Conformal Field Theory

    E-Print Network [OSTI]

    Stanford, Douglas

    We study chaotic dynamics in two-dimensional conformal field theory through out-of-time-order thermal correlators of the form ?W(t)VW(t)V?. We reproduce holographic calculations similar to those of Shenker and Stanford, ...

  13. IL NUOVO CIMENTO Vol. ?, N. ? ? New Developments in Density-Functional Theory

    E-Print Network [OSTI]

    Wasserman, Adam

    Taylor Rd., Pis- cataway, NJ 08854-8087, USA 1. ­ Introduction The theme of the present Course is "The. In physics there is a hierarchy in the scales of space and time: M-"theory", the standard model, nuclei

  14. Nonlinear electronic excitations in crystalline solids using meta-generalized gradient approximation and hybrid functional in time-dependent density functional theory

    E-Print Network [OSTI]

    Sato, Shunsuke A; Shinohara, Yasushi; Yabana, Kazuhiro

    2015-01-01

    We develop numerical methods to calculate electron dynamics in crystalline solids in real-time time-dependent density functional theory employing exchange-correlation potentials which reproduce band gap energies of dielectrics; a meta generalized gradient approximation (meta-GGA) proposed by Tran and Blaha [Phys. Rev. Lett. 102, 226401 (2009)] (TBm-BJ) and a hybrid functional proposed by Heyd, Scuseria, and Ernzerhof [J. Chem. Phys. 118, 8207 (2003)] (HSE). In time evolution calculations employing the TB-mBJ potential, we have found it necessary to adopt a predictor-corrector step for stable time-evolution. Since energy functional is not known for the TB-mBJ potential, we propose a method to evaluate electronic excitation energy without referring to the energy functional. Calculations using the HSE hybrid functional is computationally expensive due to the nonlocal Fock-like term. We develop a computational method for the operation of the Fock-like term in Fourier space, for which we employ massively parallel ...

  15. DFT --Das Future Tool ``Das Future Tool'' was the title of the group T-shirt1 that we

    E-Print Network [OSTI]

    Ziegler, Tom

    TRIBUTE DFT -- Das Future Tool ``Das Future Tool'' was the title of the group T-shirt1 that we had and considered it just another semi-empirical method.2 Tom, however, realized that DFT was ``Das Future Tool

  16. Landscape of the exact energy functional

    E-Print Network [OSTI]

    Cohen, Aron J

    2015-01-01

    One of the great challenges of electronic structure theory is the search for the exact functional of density functional theory (DFT). Its existence is undoubted but it is hard to even conceptualize it as it is a surface in a massively multidimensional space. However, the asymmetric two-site Hubbard model has a two-dimensional universe of density matrices and the exact functional simply becomes a function of two variables whose landscape can be calculated, visualized and explored. This one unique surface contains all the possible physics of any system in this universe. A walk on this landscape, moved to the angle of any one-electron Hamiltonian, gives a valley whose minimum is the exact total energy. We show concrete examples of pure-state density matrices that are not v-representable due to the underlying non-convex nature of the exact functional. Using the Perdew, Parr, Levy and Balduz extension to fractional ensembles we calculate the exact functional for all numbers of electrons. The derivative discontinui...

  17. PHYSICAL REVIEW C 77, 064308 (2008) Effective shell model Hamiltonians from density functional theory: Quadrupolar and

    E-Print Network [OSTI]

    Bertsch George F.

    2008-01-01

    ), and the configuration-interaction shell-model (CISM) approach [2]. SCMF theories are often cast in terms of an energy. Such parametrizations are usually based on the zero-range Skyrme force [3] or on the Gogny interaction [4]. The CISM effective CISM interactions can sometimes be traced back to the bare nucleon-nucleon interaction

  18. Density Functional Theory for Protein Transfer Free Energy Eric A. Mills and Steven S. Plotkin*

    E-Print Network [OSTI]

    Plotkin, Steven S.

    -solvation" repulsive force at larger distances. 1. INTRODUCTION Proteins fold and function in the crowded environment different that the conditions for protein folding are generally mutually exclusive between the two milieu environment on protein folding, stability, and function. Accurately accounting for the effects of the cell

  19. Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density: Experiments and Theory

    E-Print Network [OSTI]

    Fayer, Michael D.

    (CO2) as a function of density from low density (well below the critical density) to high densityVibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density Vibrational lifetime and spectral shift data for the asymmetric CO stretching mode of W(CO)6 in supercritical

  20. Free-energy functionals of the electrostatic potential for Poisson-Boltzmann theory

    E-Print Network [OSTI]

    Vikram Jadhao; Francisco J. Solis; Monica Olvera de la Cruz

    2013-09-26

    In simulating charged systems, it is often useful to treat some ionic components of the system at the mean-field level and solve the Poisson-Boltzmann (PB) equation to get their respective density profiles. The numerically intensive task of solving the PB equation at each step of the simulation can be bypassed using variational methods that treat the electrostatic potential as a dynamic variable. But such approaches require the access to a true free-energy functional; a functional that not only provides the correct solution of the PB equation upon extremization, it also evaluates to the true free energy of the system at its minimum. Moreover, the numerical efficiency of such procedures is further enhanced if the free-energy functional is local and is expressed in terms of the electrostatic potential. Existing PB functionals of the electrostatic potential, while possessing the local structure, are not free-energy functionals. We present a variational formulation with a local free-energy functional of the potential. In addition, we also construct a nonlocal free-energy functional of the electrostatic potential. These functionals are suited for employment in simulation schemes based on the ideas of dynamical optimization.

  1. Interaction energies of monosubstituted benzene dimers via nonlocal density functional theory

    E-Print Network [OSTI]

    T. Thonhauser; Aaron Puzder; David C. Langreth

    2005-09-15

    We present density-functional calculations for the interaction energy of monosubstituted benzene dimers. Our approach utilizes a recently developed fully nonlocal correlation energy functional, which has been applied to the pure benzene dimer and several other systems with promising results. The interaction energy as a function of monomer distance was calculated for four different substituents in a sandwich and two T-shaped configurations. In addition, we considered two methods for dealing with exchange, namely using the revPBE generalized gradient functional as well as full Hartree-Fock. Our results are compared with other methods, such as Moller-Plesset and coupled-cluster calculations, thereby establishing the usefulness of our approach. Since our density-functional based method is considerably faster than other standard methods, it provides a computational inexpensive alternative, which is of particular interest for larger systems where standard calculations are too expensive or infeasible.

  2. Structure of cylindrical electric double layers: Comparison of density functional and modified Poisson-Boltzmann theories with Monte Carlo simulations

    E-Print Network [OSTI]

    V. Dorvilien; C. N. Patra; L. B. Bhuiyan; C. W. Outhwaite

    2013-12-17

    The structure of cylindrical double layers is studied using a modified Poisson Boltzmann theory and the density functional approach. In the model double layer, the electrode is a cylindrical polyion that is infinitely long, impenetrable, and uniformly charged. The polyion is immersed in a sea of equi-sized rigid ions embedded in a dielectric continuum. An in-depth comparison of the theoretically predicted zeta potentials, the mean electrostatic potentials, and the electrode-ion singlet density distributions is made with the corresponding Monte Carlo simulation data. The theories are seen to be consistent in their predictions that include variations in ionic diameters, electrolyte concentrations, and electrode surface charge densities, and are also capable of well reproducing some new and existing Monte Carlo results.

  3. Applicability of Density Functional Theory in Reproducing Accurate Vibrational Spectra of Surface Bound Species

    SciTech Connect (OSTI)

    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 Schr€odinger 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.

  4. Impaired Theory Of Mind for Moral Judgment in High-Functioning Autism

    E-Print Network [OSTI]

    Moran, Joseph M.

    High-functioning autism (ASD) is characterized by real-life difficulties in social interaction; however, these individuals often succeed on laboratory tests that require an understanding of another person's beliefs and ...

  5. Fourier Theory on the Complex Plane I: Conjugate Pairs of Fourier Series and Inner Analytic Functions

    E-Print Network [OSTI]

    Jorge L. deLyra

    2015-03-24

    A correspondence between arbitrary Fourier series and certain analytic functions on the unit disk of the complex plane is established. The expression of the Fourier coefficients is derived from the structure of complex analysis. The orthogonality and completeness relations of the Fourier basis are derived in the same way. It is shown that the limiting function of any Fourier series is also the limit to the unit circle of an analytic function in the open unit disk. An alternative way to recover the original real functions from the Fourier coefficients, which works even when the Fourier series are divergent, is thus presented. The convergence issues are discussed up to a certain point. Other possible uses of the correspondence established are pointed out.

  6. Analysis of smart functionally graded materials using an improved third order shear deformation theory 

    E-Print Network [OSTI]

    Aliaga Salazar, James Wilson

    2009-06-02

    Smart materials are very important because of their potential applications in the biomedical, petroleum and aerospace industries. They can be used to build systems and structures that self-monitor to function and adapt to new operating conditions...

  7. Of energy and the economy : theory and evidence for their functional relationship

    E-Print Network [OSTI]

    Chang, Vincent H. (Vincent Hua-Cheng)

    2007-01-01

    This paper offers a set of explicit functional relationships that link energy and the economy. Despite the reliance on energy permeating the whole economy, no such complete relationships had been presented before. How ...

  8. Non-monotonic Lyapunov functions for stability of nonlinear and switched systems : theory and computation

    E-Print Network [OSTI]

    Ahmadi, Amir Ali

    2008-01-01

    Lyapunov's direct method, which is based on the existence of a scalar function of the state that decreases monotonically along trajectories, still serves as the primary tool for establishing stability of nonlinear systems. ...

  9. Coulomb gauge Green functions and Gribov copies in SU(2) lattice gauge theory

    E-Print Network [OSTI]

    M. Quandt; G. Burgio; S. Chimchinda; H. Reinhardt

    2007-10-02

    We reconsider the lattice measurement of Green functions in Coulomb gauge, both in 2+1 and 3+1 dimensions, using an improved gauge fixing scheme. The influence of Gribov copies is examined and we find clear indications that Green functions are more strongly affected than previously assumed, in particular for low momenta. Qualitatively, our improved lattice results in the infra-red compare more favourably with recent continuum calculations in the Hamiltonian approach.

  10. Fourier Theory on the Complex Plane IV: Representability of Real Functions by their Fourier Coefficients

    E-Print Network [OSTI]

    Jorge L. deLyra

    2015-05-04

    The results presented in this paper are refinements of some results presented in a previous paper. Three such refined results are presented. The first one relaxes one of the basic hypotheses assumed in the previous paper, and thus extends the results obtained there to a wider class of real functions. The other two relate to a closer examination of the issue of the representability of real functions by their Fourier coefficients. As was shown in the previous paper, in many cases one can recover the real function from its Fourier coefficients even if the corresponding Fourier series diverges almost everywhere. In such cases we say that the real function is still representable by its Fourier coefficients. Here we establish a very weak condition on the Fourier coefficients that ensures the representability of the function by those coefficients. In addition to this, we show that any real function that is absolutely integrable can be recovered almost everywhere from, and hence is representable by, its Fourier coefficients, regardless of whether or not its Fourier series converges. Interestingly, this also provides proof for a conjecture proposed in the previous paper.

  11. Deriving the quark condensate within a finite Fermi system from the generating functional of chiral perturbation theory

    E-Print Network [OSTI]

    Mariana Kirchbach; Andreas Wirzba

    1996-11-01

    The generating functional of heavy baryon chiral perturbation theory at order O(Q^2) in the mean field approximation (with a pseudoscalar source coupling which is consistent with the PCAC-Ward identities on the current quark level) has been exploited to derive Migdal's in--medium pion propagator. It is shown that the prediction for the density dependence of the quark condensate obtained on the composite hadron level by embedding PCAC within the framework of Migdal's approach to finite Fermi systems is identical to that resulting from QCD.

  12. Deriving the quark condensate within a finite Fermi system from the generating functional of chiral perturbation theory

    E-Print Network [OSTI]

    Kirchbach, M; Kirchbach, Mariana; Wirzba, Andreas

    1996-01-01

    The generating functional of heavy baryon chiral perturbation theory at order {\\cal O}(Q^2) in the mean field approximation (with a pseudoscalar source coupling which is consistent with the PCAC-Ward identities on the current quark level) has been exploited to derive Migdal's in--medium pion propagator. It is shown that the prediction for the density dependence of the quark condensate obtained on the composite hadron level by embedding PCAC within the framework of Migdal's approach to finite Fermi systems is identical to that resulting from QCD.

  13. Hetero-twin formation during growth of nano-scale Al-TiN composites - experimental and DFT studies

    SciTech Connect (OSTI)

    Bhattacharyya, Dhriti [Los Alamos National Laboratory; Liu, Xiang - Yang [Los Alamos National Laboratory; Hoagland, Richard G [Los Alamos National Laboratory; Misra, Amit [Los Alamos National Laboratory; Genc, A [MSE, OSU; Fraser, H L [MSE, OSU

    2009-01-01

    It is well known that high stacking fault energy metals such as Al do not form either growth twins or mechanical twins easily. Although mechanical twins in nanocrystalline Al have been observed under certain conditions, growth twins have never been observed. In this work, the authors report for the first time, through transmission electron microscopy (TEM), that Al layers, when deposited on TiN layers, tend to grow in a twin relationship to both the TiN layer and the underlying Al layer. The TiN layers assume the orientation of the Al layers below. Calculations using density functional theory (DFT) show that nitrogen termination in the {l_brace}111{r_brace} growth plane of the TiN layers favors the growth of twin oriented Al layers over these TiN layers. This finding provides a way to create a twin-modulated structure in Al with the inclusion of intermediate nm-scale layer of an ionic solid such as TiN. Al metal is resistant to twinning, as it has a high stacking fault energy (SFE) of > 150 mJ/m. Although twins have been observed in nano-scale grains of Al, and predicted by molecular dynamics (MD) simulations in conditions when the nanoscale grains are plastically deformed, no process or phenomenon has been reported yet in which the deposition of an intermediate layer of a different material phase causes the subsequent layer of Al to be deposited in the twin orientation. The authors show in this paper that it is possible to form Al layers in twin orientation to each other across polar TiN layers, if these are grown so that both the Al and TiN layers have a {l_brace}111{r_brace} surface as their growth front. Since the deposition of Al and TiN layers is used in the formation of diffusion barriers, and the mechanical properties of these nanoscale multilayers are also seen to be exceptional, it is important to investigate and understand their structure at the nanometer length scale, and thence to be able to control it. Moreover, these findings point out a method of introducing nano-scale twins in high SFE materials in general, and can potentially improve the properties of nano-layered materials.

  14. On the contact values of the density profiles in an electric double layer using density functional theory

    E-Print Network [OSTI]

    L. B. Bhuiyan; D. Henderson; S. Soko?owski

    2012-07-13

    A recently proposed local second contact value theorem [Henderson D., Boda D., J. Electroanal. Chem., 2005, 582, 16] for the charge profile of an electric double layer is used in conjunction with the existing Monte Carlo data from the literature to assess the contact behavior of the electrode-ion distributions predicted by the density functional theory. The results for the contact values of the co- and counterion distributions and their product are obtained for the symmetric valency, restricted primitive model planar double layer for a range of electrolyte concentrations and temperatures. Overall, the theoretical results satisfy the second contact value theorem reasonably well, the agreement with the simulations being semi-quantitative or better. The product of the co- and counterion contact values as a function of the electrode surface charge density is qualitative with the simulations with increasing deviations at higher concentrations.

  15. Searching for 4$?$ linear-chain structure in excited states of $^{16}$O with a covariant density functional theory

    E-Print Network [OSTI]

    J. M. Yao; N. Itagaki; J. Meng

    2014-09-19

    A study of 4$\\alpha$ linear-chain structure in high-lying collective excitation states of $^{16}$O with a covariant density functional theory is presented. The low-spin states are obtained by configuration mixing of particle-number and angular-momentum projected quadrupole deformed mean-field states with generator coordinate method. The high-spin states are determined by cranking calculations. These two calculations are based on the same energy density functional PC-PK1. We have found a rotational band at low-spin with the dominated intrinsic configuration considered to be the one that 4$\\alpha$ clusters stay along a common axis. The strongly deformed rod shape also appears in the high-spin region with the angular momentum $13-18\\hbar$; however whether the state is pure $4\\alpha$ linear chain or not is less obvious than that in the low-spin states.

  16. Fast Computation of Solvation Free Energies with Molecular Density Functional Theory: Thermodynamic-Ensemble Partial Molar Volume Corrections

    E-Print Network [OSTI]

    Volodymyr P. Sergiievskyi; Guillaume Jeanmairet; Maximilien Levesque; Daniel Borgis

    2014-06-11

    Molecular Density Functional Theory (MDFT) offers an efficient implicit- solvent method to estimate molecule solvation free-energies whereas conserving a fully molecular representation of the solvent. Even within a second order ap- proximation for the free-energy functional, the so-called homogeneous reference uid approximation, we show that the hydration free-energies computed for a dataset of 500 organic compounds are of similar quality as those obtained from molecular dynamics free-energy perturbation simulations, with a computer cost reduced by two to three orders of magnitude. This requires to introduce the proper partial volume correction to transform the results from the grand canoni- cal to the isobaric-isotherm ensemble that is pertinent to experiments. We show that this correction can be extended to 3D-RISM calculations, giving a sound theoretical justifcation to empirical partial molar volume corrections that have been proposed recently.

  17. Joint Density-Functional Theory of Electrochemistry > Research Highlights >

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfateSciTechtail.Theory ofDid you notHeat Pumps HeatTechnologies | Blandine| Blandine|In This

  18. Communication: Self-interaction correction with unitary invariance in density functional theory

    SciTech Connect (OSTI)

    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.

  19. Systematization of Basic Divergent Integrals in Perturbation Theory and Renormalization Group Functions

    E-Print Network [OSTI]

    L. C. T. Brito; H. G. Fargnoli; A. P. Baêta Scarpelli; Marcos Sampaio; M. C. Nemes

    2009-03-12

    We show that to n loop order the divergent content of a Feynman amplitude is spanned by a set of basic (logarithmically divergent) integrals which need not be evaluated. Only the coefficients of the basic divergent integrals are necessary to determine renormalization group functions. Relations between these coefficients of different loop orders are derived.

  20. The Fourier transform solution for the Green's function of monoenergetic neutron transport theory

    E-Print Network [OSTI]

    Barry D. ganapol

    2014-03-17

    Nearly 45 years ago, Ken Case published his seminal paper on the singular eigenfunction solution for the Green's function of the monoenergetic neutron transport equation with isotropic scattering. Previously, the solution had been obtained by Fourier transform. While it is apparent the two had to be equivalent, a convincing equivalence proof for general anisotropic scattering remained a challenge until now.

  1. Generalized coherent-state derivation of time-dependent density-functional theory equations for superconductors

    E-Print Network [OSTI]

    Mukamel, Shaul

    for superconductors Oleg Berman1, * and Shaul Mukamel1,2, 1 Department of Chemistry, University of Rochester, Box-temperature superconductors. The temperature of the Kosterlitz- Thouless transition to the two-dimensional superfluidity for the ground-state wave function of superconductors predicts a gap in the spectrum1 originating from

  2. Smooth Morse-Lyapunov Functions and Morse Theory of Strong Attractors for Nonsmooth Dynamical Systems

    E-Print Network [OSTI]

    Desheng Li

    2010-05-26

    In this paper we first construct smooth Morse-Lyapunov functions of attractors for nonsmooth dynamical systems. Then we prove that all open attractor neighborhoods of an attractor have the same homotopy type. Based on this basic fact we finally introduce the concept of critical group for Morse sets of an attractor and establish Morse inequalities and equations.

  3. On the Design of Loss Functions for Classification: theory, robustness to outliers, and SavageBoost

    E-Print Network [OSTI]

    Vasconcelos, Nuno M.

    state­of­the­art classifier design algorithms, including SVMs, boosting, and logistic regression, de literature. We show that the two problems are identical, and probability elicitation can be seen as a reverse, not the case for the reverse progression: it is shown that any functional form

  4. On the Design of Loss Functions for Classification: theory, robustness to outliers, and SavageBoost

    E-Print Network [OSTI]

    Vasconcelos, Nuno M.

    state-of-the-art classifier design algorithms, including SVMs, boosting, and logistic regression, de literature. We show that the two problems are identical, and probability elicitation can be seen as a reverse, not the case for the reverse progression: it is shown that any functional form of the minimum conditio

  5. Multiresolution quantum chemistry in multiwavelet bases: Analytic derivatives for HartreeFock and density functional theory

    E-Print Network [OSTI]

    Beylkin, Gregory

    Multiresolution quantum chemistry in multiwavelet bases: Analytic derivatives for Hartree An efficient and accurate analytic gradient method is presented for Hartree­Fock and density functional differential equations. In this paper, we extend the approach to include computation of analytic derivatives

  6. Microscopically-constrained Fock energy density functionals from chiral effective field theory. I. Two-nucleon interactions

    E-Print Network [OSTI]

    B. Gebremariam; S. K. Bogner; T. Duguet

    2010-03-26

    The density matrix expansion (DME) of Negele and Vautherin is a convenient tool to map finite-range physics associated with vacuum two- and three-nucleon interactions into the form of a Skyme-like energy density functional (EDF) with density-dependent couplings. In this work, we apply the improved formulation of the DME proposed recently in arXiv:0910.4979 by Gebremariam {\\it et al.} to the non-local Fock energy obtained from chiral effective field theory (EFT) two-nucleon (NN) interactions at next-to-next-to-leading-order (N$^2$LO). The structure of the chiral interactions is such that each coupling in the DME Fock functional can be decomposed into a cutoff-dependent coupling {\\it constant} arising from zero-range contact interactions and a cutoff-independent coupling {\\it function} of the density arising from the universal long-range pion exchanges. This motivates a new microscopically-guided Skyrme phenomenology where the density-dependent couplings associated with the underlying pion-exchange interactions are added to standard empirical Skyrme functionals, and the density-independent Skyrme parameters subsequently refit to data. A Mathematica notebook containing the novel density-dependent couplings is provided.

  7. Bethe ansatz density-functional theory of ultracold repulsive fermions in one-dimensional optical lattices

    SciTech Connect (OSTI)

    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.

  8. Redox Potentials and Acidity Constants from Density Functional Theory Based Molecular Dynamics

    E-Print Network [OSTI]

    Cheng, Jun; Liu, Xiandong; VandeVondele, Joost; Sulpizi, Marialore; Sprik, Michiel

    2014-11-03

    . Critical error anal- ysis will be carried out to demonstrate how the delocalization error in GGAs affects redox potentials. The improvement by hybrid functionals reinforces this claim. We will end this Account with some conclusions and an outlook. Method... and theoretical (photo-)electrochemistry and catalysis. Xiandong Liu is an associate professor at Nanjing University. He joined the Sprik group at Cambridge in 2012 to work on computational geochemistry of mineral interfaces and transition metal complexes. Joost...

  9. Non-Gaussian halo mass function and non-spherical halo collapse: theory vs. simulations

    SciTech Connect (OSTI)

    Achitouv, Ixandra E.; Corasaniti, Pier Stefano, E-mail: Ixandra.Achitouv@obspm.fr, E-mail: Pier-Stefano.Corasaniti@obspm.fr [Laboratoire Univers et Théories (LUTh), UMR 8102 CNRS, Observatoire de Paris, Université Paris Diderot, 5 Place Jules Janssen, 92190 Meudon (France)

    2012-02-01

    The mass distribution of dark matter halos is a sensitive probe of primordial non-Gaussianity (NG). We derive an analytical formula of the halo mass function by perturbatively computing excursion set path-integrals for a non-Gaussian density field with non-vanishing skewness, f{sub NL}. We assume a stochastic barrier model which captures the main features of the ellipsoidal collapse of halos. Contrary to previous results based on extensions of the Press-Schechter formalism to NG initial conditions, we find that the non-spherical collapse of halos directly alter the signature of primordial NG. This points toward a potential degeneracy between the effect of primordial non-Gaussianity and that of non-linear halo collapse. The inferred mass function is found to be in remarkable agreement with N-body simulations of NG local type. Deviations are well within numerical uncertainties for all values of f{sub NL}{sup loc} in the range of validity of the perturbative calculation (|f{sub nl}{sup loc}|?<200). Moreover, the comparison with simulation results suggests that for |f{sub NL}|?>30 the non-linear collapse of halos, as described by our barrier model, strongly deviates from that of Gaussian initial conditions. This is not surprising since the effect of non-linear gravitational processes may be altered by initially large NG. Hence, in the lack of prior theoretical knowledge, halo collapse model parameters should be included in statistical halo mass function data analysis which aim to constrain the signature of primordial NG.

  10. Towards time-dependent current-density-functional theory in the non-linear regime

    E-Print Network [OSTI]

    Escartín, J. M.; Vincendon, M.; Romaniello, P.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.

    2015-02-27

    ? ? Im [???(r, t)???(r, t)] ? q mc AS(r, t) ?(r, t) , (2b) and are independent of the gauge chosen to represent the electromagnetic potentials. A. The Vignale-Kohn functional in real time Up to second order in spatial derivatives, under the basic... that, while treat- ing the memory instantaneously in time, maintains the dissipating effects of the VK approximation. We have demonstrated the capabilities of the method by apply- ing it to Mg, Ca and Na2 whereby we are modeling a short laser pulse...

  11. Determining Importance Weighting Functions for Contributon Theory Eigenvalue Sensitivity Coefficient Methodologies

    SciTech Connect (OSTI)

    Perfetti, Christopher M [ORNL] [ORNL; Martin, William R [University of Michigan] [University of Michigan; Rearden, Bradley T [ORNL] [ORNL; Williams, Mark L [ORNL] [ORNL

    2012-01-01

    This study introduced three approaches for calculating the importance weighting function for Contributon and CLUTCH eigenvalue sensitivity coefficient calculations, and compared them in terms of accuracy and applicability. The necessary levels of mesh refinement and mesh convergence for obtaining accurate eigenvalue sensitivity coefficients were determined through two parametric studies, and the results of these studies suggest that a sufficiently-accurate mesh for calculating eigenvalue sensitivity coefficients can be obtained for the Contributon and CLUTCH methods with only a small increase in problem runtime.

  12. 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

  13. The Spacetime of Double Field Theory: Review, Remarks, and Outlook

    E-Print Network [OSTI]

    Olaf Hohm; Dieter Lust; Barton Zwiebach

    2014-10-30

    We review double field theory (DFT) with emphasis on the doubled spacetime and its generalized coordinate transformations, which unify diffeomorphisms and b-field gauge transformations. We illustrate how the composition of generalized coordinate transformations fails to associate. Moreover, in dimensional reduction, the O(d,d) T-duality transformations of fields can be obtained as generalized diffeomorphisms. Restricted to a half-dimensional subspace, DFT includes `generalized geometry', but is more general in that local patches of the doubled space may be glued together with generalized coordinate transformations. Indeed, we show that for certain T-fold backgrounds with non-geometric fluxes, there are generalized coordinate transformations that induce, as gauge symmetries of DFT, the requisite O(d,d;Z) monodromy transformations. Finally we review recent results on the \\alpha' extension of DFT which, reduced to the half-dimensional subspace, yields intriguing modifications of the basic structures of generalized geometry.

  14. Continuum quasiparticle linear response theory using the Skyrme functional for multipole responses of exotic nuclei

    E-Print Network [OSTI]

    Kazuhito Mizuyama; Masayuki Matsuo; Yasuyoshi Serizawa

    2009-01-12

    We develop a new formulation of the continuum quasiparticle random phase approximation (QRPA) in which the residual interaction is derived directly from the Skyrme energy functional, keeping all the velocity dependent terms of the Skyrme effective interaction. Numerical analysis using the SkM$^*$ parameter set is performed for the isovector dipole and the isovector/isoscalar quadrupole responses in $^{20}$O and $^{54}$Ca. It is shown that the energy-weighted sum rule including the enhancement factors for the isovector responses is satisfied with good accuracy. We investigate also how the velocity dependent terms influence the strength distribution and the transition densities of the low-lying surface modes and the giant resonances.

  15. Semi-microscopic modeling of heavy-ion fusion reactions with multi-reference covariant density functional theory

    E-Print Network [OSTI]

    K. Hagino; J. M. Yao

    2015-04-15

    We describe low-lying collective excitations of atomic nuclei with the multi-reference covariant density functional theory, and combine them with coupled-channels calculations for heavy-ion fusion reactions at energies around the Coulomb barrier. To this end, we use the calculated transition strengths among several collective states as inputs to the coupled-channels calculations. This approach provides a natural way to describe anharmonic multi-phonon excitations as well as a deviation of rotational excitations from a simple rigid rotor. We apply this method to subbarrier fusion reactions of $^{58}$Ni+$^{58}$Ni, $^{58}$Ni+$^{60}$Ni and $^{40}$Ca+$^{58}$Ni systems. We find that the effect of anharmonicity tends to smear the fusion barrier distributions, better reproducing the experimental data compared to the calculations in the harmonic oscillator limit.

  16. Electrons as probes of dynamics in molecules and clusters : a contribution from Time Dependent Density Functional Theory

    E-Print Network [OSTI]

    Wopperer, P; Reinhard, P -G; Suraud, E

    2014-01-01

    Various ways to analyze the dynamical response of clusters and molecules to electromagnetic perturbations exist. Particularly rich information can be obtained from measuring the properties of electrons emitted in the course of the excitation dynamics. Such an analysis of electron signals covers total ionization, Photo-Electron Spectra, Photoelectron Angular Distributions, and ideally combined PES/PAD, with a long history in molecular physics, also increasingly used in cluster physics. Recent progress in the design of new light sources (high intensity and/or frequency, ultra short pulses) opens new possibilities for measurements and thus has renewed the interest on the analysis of dynamical scenarios through these observables, well beyond a simple access to a density of states. This, in turn, has motivated many theoretical investigations of the dynamics of electronic emission for molecules and clusters. A theoretical tool of choice is here Time-Dependent Density Functional Theory (TDDFT) propagated in real tim...

  17. Electronic density-of-states of amorphous vanadium pentoxide films: Electrochemical data and density functional theory calculations

    SciTech Connect (OSTI)

    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.

  18. Combining linear interpolation with extrapolation methods in range-separated ensemble density-functional theory

    E-Print Network [OSTI]

    Senjean, Bruno; Alam, Md Mehboob; Knecht, Stefan; Fromager, Emmanuel

    2015-01-01

    The combination of a recently proposed linear interpolation method (LIM) [Senjean et al., Phys. Rev. A 92, 012518 (2015)], which enables the calculation of weight-independent excitation energies in range-separated ensemble density-functional approximations, with the extrapolation scheme of Savin [J. Chem. Phys. 140, 18A509 (2014)] is presented in this work. It is shown that LIM excitation energies vary quadratically with the inverse of the range-separation parameter mu when the latter is large. As a result, the extrapolation scheme, which is usually applied to long-range interacting energies, can be adapted straightforwardly to LIM. This extrapolated LIM (ELIM) has been tested on a small test set consisting of He, Be, H2 and HeH+. Relatively accurate results have been obtained for the first singlet excitation energies with the typical mu=0.4 value. The improvement of LIM after extrapolation is remarkable, in particular for the doubly-excited 2^1Sigma+g state in the stretched H2 molecule. Three-state ensemble ...

  19. Scalar relativistic computations of nuclear magnetic shielding and g-shifts with the zeroth-order regular approximation and range-separated hybrid density functionals

    SciTech Connect (OSTI)

    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.

  20. Fundamental measure theory for the electric double layer: implications for blue-energy harvesting and water desalination

    E-Print Network [OSTI]

    Andreas Härtel; Mathijs Janssen; Sela Samin; René van Roij

    2015-03-06

    Capacitive mixing (CAPMIX) and capacitive deionization (CDI) are promising candidates for harvesting clean, renewable energy and for the energy efficient production of potable water, respectively. Both CAPMIX and CDI involve water-immersed porous carbon (supercapacitors) electrodes at voltages of the order of hundreds of millivolts, such that counter-ionic packing is important for the electric double layer (EDL) which forms near the surface of these porous materials. Thus, we propose a density functional theory (DFT) to model the EDL, where the White-Bear mark II fundamental measure theory functional is combined with a mean-field Coulombic and a mean spherical approximation-type correction to describe the interplay between dense packing and electrostatics, in good agreement with molecular dynamics simulations. We discuss the concentration-dependent potential rise due to changes in the chemical potential in capacitors in the context of an over-ideal theoretical description and its impact on energy harvesting and water desalination. Compared to less elaborate mean-field models our DFT calculations reveal a higher work output for blue-energy cycles and a higher energy demand for desalination cycles.

  1. Distinguishing tautomerism in the crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide using DFT-D calculations and {sup 13}C solid-state NMR

    SciTech Connect (OSTI)

    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.

  2. Time-dependent density-functional theory for strong-field multiphoton processes: Application to the study of the role of dynamical electron correlation in multiple high-order harmonic generation

    E-Print Network [OSTI]

    Tong, Xiao-Min; Chu, Shih-I

    1998-01-01

    We present a self-interaction-free time-dependent density-functional theory (TDDFT) for nonperturbative treatment of multiphoton processes of many-electron atomic systems in intense laser fields. The theory is based on the ...

  3. Electron dynamics in complex environments with real-time time dependent density functional theory in a QM-MM framework

    SciTech Connect (OSTI)

    Morzan, Uriel N.; Ramírez, Francisco F.; Scherlis, Damián A. E-mail: mcgl@qb.ffyb.uba.ar; Lebrero, Mariano C. González 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 matrix—required 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.

  4. Density functional theory calculations of the turbostratically disordered compound [(SnSe)1+y]m(VSe2)n

    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

  5. Testing time-dependent density functional theory with depopulated molecular orbitals for predicting electronic excitation energies of valence, Rydberg, and charge-transfer

    E-Print Network [OSTI]

    Truhlar, Donald G

    transition energies J. Chem. Phys. 137, 244104 (2012); 10.1063/1.4769078 A long-range-corrected densityTesting time-dependent density functional theory with depopulated molecular orbitals for predicting electronic excitation energies of valence, Rydberg, and charge-transfer states and potential energies near

  6. Density functional theory study of first-layer adsorption of ZrO2 and HfO2 on Ge(100)

    E-Print Network [OSTI]

    Kummel, Andrew C.

    in this manuscript), usually grown by atomic layer deposition (ALD). These oxides, under normal Ge process- ingDensity functional theory study of first-layer adsorption of ZrO2 and HfO2 on Ge(100) T.J. Grassman

  7. PdnCO (n ) 1,2): Accurate Ab Initio Bond Energies, Geometries, and Dipole Moments and the Applicability of Density Functional Theory for Fuel Cell Modeling

    E-Print Network [OSTI]

    Gherman, Benjamin F.

    and the Applicability of Density Functional Theory for Fuel Cell Modeling Nathan E. Schultz, Benjamin F. Gherman Form: August 18, 2006 Electrode poisoning by CO is a major concern in fuel cells. As interest. Introduction Several of the most successful fuel cell applications use a Pt anode as a catalyst

  8. Final Technical Report for DE-SC0001878 [Theory and Simulation of Defects in Oxide Materials

    SciTech Connect (OSTI)

    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.

  9. "Kohn-Shamification" of the classical density-functional theory of inhomogeneous polar molecular liquids with application to liquid hydrogen chloride

    E-Print Network [OSTI]

    Johannes Lischner; T. A. Arias

    2008-06-27

    The Gordian knot of density-functional theories for classical molecular liquids remains finding an accurate free-energy functional in terms of the densities of the atomic sites of the molecules. Following Kohn and Sham, we show how to solve this problem by considering noninteracting molecules in a set of effective potentials. This shift in perspective leads to an accurate and computationally tractable description in terms of simple three-dimensional functions. We also treat both the linear- and saturation- dielectric responses of polar systems, presenting liquid hydrogen chloride as a case study.

  10. Application of the Theory of Linear Singular Integral Equations to a Riemann Hilbert Problem for a New Expression of Chandrasekhar's H- function in Radiative Transfer

    E-Print Network [OSTI]

    Rabindra Nath Das

    2007-01-16

    The linear non homogeneous singular integral equation (LNSIE)derived from the nonlinear non homogeneous integral eauation (NNIE)of Chandrsasekhar's H- functions is considered here to develop a new form of H - functions.The Plemelj's formulae are applied to that equation to determine a new linear non homogeneous integral equation(LNIE)for H- functions in complex plane . The analytic properties of this new linear integral equation are assessed and compared with known linear integral equations satisfied by H- functions. The Cauchy integral formulae in complex plane are used to obtain this form of H- functions not dependent on H- function in the integral . This new form of H-function is represented as a simple integral in terms of known functions both for conservative and non conservative cases. This is identical with the form of H- functions derived by this author by application of Wiener HOpf technique. The equivalence of application of the theory of linear singular integral equation in Riemann Hilbert Problem and of the technique of Wiener- Hopf in linear integral in representing the H- functions is therefore eatablished .This new form may be used for solving the problems of radiative transfer in anisotropic and non coherent scattering by the method of Laplace Transform and Wiener -Hopf technique.

  11. DFT study of the interaction between guanine and water A.K. Chandraa

    E-Print Network [OSTI]

    Nguyen, Minh Tho

    . Uchimarua , Th. Zeegers-Huyskensb,* a Department of Physical Chemistry, National Institute of Materials(d,p) basis set. The results obtained with geometry optimization (FULL) made without any constraint rights reserved. Keywords: Geometry optimization; Density functional theory; Guanine­water complex 1

  12. A density functional theory study of the oxidation of methanol to formaldehyde over vanadia supported on silica, titania, and zirconia

    SciTech Connect (OSTI)

    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.

  13. with statistically independent nonredundant coefficientsdue to the linearity of the DFT.

    E-Print Network [OSTI]

    Teich, Malvin C.

    with statistically independent nonredundant coefficientsdue to the linearity of the DFT. 2 5 P. D.Welch,"The useof Fast FourierTransform for the estimation of power spectra: A method based on time averaging over to produce impulses during the refractory period do not prolong the duration of the period (nonparalyzable

  14. An Efficient Arithmetic Sum-of-Product (SOP) based Multiplication Approach for FIR Filters and DFT 

    E-Print Network [OSTI]

    Kumar, Rajeev

    2013-04-24

    -arriving lower-order bits, a Kogge-Stone adder for the slower middle bits, and a carry-select adder for the early-arriving higher order bits). The DFT and FIR filters can also be cast as instances of the Multiple Constant Multiplication (MCM) problem. RAG...

  15. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    SciTech Connect (OSTI)

    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 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.

  16. Quantum-Based Theories of Condensed Matter Emily A. Carter

    E-Print Network [OSTI]

    Simons, Jack

    , 2005 "Stainless steel optimization from DFT", Vitos et al., Nature: materials, 2002 "Interface between & Spin-Dependent Pseudopotential Theory for Open-Shell and Magnetic Systems - Materials Applications - Quantum-Based Multiscale Modeling of Materials For talk #1, thanks to: Dr. Vincent Cocula (COMSOL, Inc

  17. 422 IEEE TRANSACTIONS ON INFORMATION THEORY, VOL. 60, NO. 1, JANUARY 2014 Computing Linear Functions by Linear Coding

    E-Print Network [OSTI]

    Franceschetti, Massimo

    Functions by Linear Coding Over Networks Rathinakumar Appuswamy, Member, IEEE, and Massimo Franceschetti and a receiver node demands an arbi- trary linear function of these messages. We formulate an algebraic test to determine whether an arbitrary network can compute linear functions using linear codes. We identify a class

  18. Towards a specific reaction parameter density functional for reactive scattering of H{sub 2} from Pd(111)

    SciTech Connect (OSTI)

    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 Born–Oppenheimer 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.

  19. The Asymptotics of the Correlations Functions in $(1+1)d$ Quantum Field Theory From Finite Size Effects in Conformal Theories

    E-Print Network [OSTI]

    A. Mironov; A. Zabrodin

    1992-01-08

    Using the finite-size effects the scaling dimensions and correlation functions of the main operators in continuous and lattice models of 1d spinless Bose-gas with pairwise interaction of rather general form are obtained. The long-wave properties of these systems can be described by the Gaussian model with central charge $c=1$. The disorder operators of the extended Gaussian model are found to correspond to some non-local operators in the {\\it XXZ} Heisenberg antiferromagnet. Just the same approach is applicable to fermionic systems. Scaling dimensions of operators and correlation functions in the systems of interacting Fermi-particles are obtained. We present a universal treatment for $1d$ systems of different kinds which is independent of the exact integrability and gives universal expressions for critical exponents through the thermodynamic characteristics of the system.

  20. Revisiting HgCl2: A Solution- and Solid-State 199Hg NMR and ZORA-DFT Computational Study

    E-Print Network [OSTI]

    Taylor, Robert E; Carver, Colin T; Larsen, Ross E; Dmitrenko, Olga; Bai, Shi; Dybowski, Cecil

    2009-01-01

    7 (1997), 333-336. [26] R. E. Taylor, Concepts Magn. Reson.DFT Computational Study R. E. Taylor 1 *, Colin T. Carver2522 USA *Corresponding author: R. E. Taylor Email address:

  1. DFT STUDY REVISES INTERSTITIAL CONFIGURATIONS IN HCP Zr

    SciTech Connect (OSTI)

    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.

  2. Ab initio density functional theory investigation of the structural, electronic and optical properties of Ca{sub 3}Sb{sub 2} in hexagonal and cubic phases

    SciTech Connect (OSTI)

    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 exchange–correlation 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.

  3. Electromagnetic Theory 1 /56 Electromagnetic Theory

    E-Print Network [OSTI]

    Bicknell, Geoff

    Electromagnetic Theory 1 /56 Electromagnetic Theory Summary: · Maxwell's equations · EM Potentials · Equations of motion of particles in electromagnetic fields · Green's functions · Lienard-Weichert potentials · Spectral distribution of electromagnetic energy from an arbitrarily moving charge #12;Electromagnetic

  4. Self-interaction-free time-dependent density-functional theory for molecular processes in strong fields:? High-order harmonic generation of H2 in intense laser fields

    E-Print Network [OSTI]

    Chu, Shih-I; Chu, Xi

    2001-01-17

    We present a self-interaction-free time-dependent density-functional theory (TDDFT) for nonperturbative treatment of multiphoton processes of many-electron molecular systems in intense laser fields. The time-dependent ...

  5. Time-dependent density-functional theory for molecular processes in strong fields: Study of multiphoton processes and dynamical response of individual valence electrons of N2 in intense laser fields

    E-Print Network [OSTI]

    Chu, Xi; Chu, Shih-I

    2001-11-14

    We present a time-dependent density-functional theory (TDDFT) with proper asymptotic long-range potential for nonperturbative treatment of multiphoton processes of many-electron molecular systems in intense laser fields. ...

  6. A density functional theory study of magneto-electric Jones birefringence of noble gases, furan homologues, and mono-substituted benzenes

    SciTech Connect (OSTI)

    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.

  7. Spin and orbital magnetism of coinage metal trimers (Cu{sub 3}, Ag{sub 3}, Au{sub 3}): A relativistic density functional theory study

    SciTech Connect (OSTI)

    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.

  8. Five-loop additive renormalization in the phi^4 theory and amplitude functions of the minimally renormalized specific heat in three dimensions

    E-Print Network [OSTI]

    S. A. Larin; M. Moennigmann; M. Stroesser; V. Dohm

    1997-11-07

    We present an analytic five-loop calculation for the additive renormalization constant A(u,epsilon) and the associated renormalization-group function B(u) of the specific heat of the O(n) symmetric phi^4 theory within the minimal subtraction scheme. We show that this calculation does not require new five-loop integrations but can be performed on the basis of the previous five-loop calculation of the four-point vertex function combined with an appropriate identification of symmetry factors of vacuum diagrams. We also determine the amplitude functions of the specific heat in three dimensions for n=1,2,3 above T_c and for n=1 below T_c up to five-loop order. Accurate results are obtained from Borel resummations of B(u) for n=1,2,3 and of the amplitude functions for n=1. Previous conjectures regarding the smallness of the resummed higher-order contributions are confirmed. Borel resummed universal amplitude ratios A^+/A^- and a_c^+/a_c^- are calculated for n=1.

  9. van der Waals density functionals built upon the electron-gas tradition: Facing the challenge of competing interactions

    SciTech Connect (OSTI)

    Berland, Kristian [Chalmers University of Technology, Sweden] [Chalmers University of Technology, Sweden; Arter, Calvin A [Wake Forest University, Winston-Salem] [Wake Forest University, Winston-Salem; Cooper, Valentino R [ORNL] [ORNL; Lee, Dr. Kyuho [Lawrence Berkeley National Laboratory (LBNL)] [Lawrence Berkeley National Laboratory (LBNL); Lundqvist, Prof. Bengt I. [Chalmers University of Technology, Sweden] [Chalmers University of Technology, Sweden; Schroder, Prof. Elsebeth [Chalmers University of Technology, Sweden] [Chalmers University of Technology, Sweden; Thonhauser, Prof. Timo [Wake Forest University, Winston-Salem] [Wake Forest University, Winston-Salem; Hyldgaard, Per [Chalmers University of Technology, Sweden] [Chalmers University of Technology, Sweden

    2014-01-01

    The theoretical description of sparse matter attracts much interest, in particular for those groundstate properties that can be described by density functional theory (DFT). One proposed approach, the van der Waals density functional (vdW-DF) method, rests on strong physical foundations and offers simple yet accurate and robust functionals. A very recent functional within this method called vdW-DF-cx [K. Berland and P. Hyldgaard, Phys. Rev. B, in print] stands out in its attempt to use an exchange energy derived from the same plasmon-based theory from which the nonlocal correlation energy was derived. Encouraged by its good performance for solids, layered materials, and aromatic molecules, we apply it to several systems that are characterized by competing interactions. These include the ferroelectric response in PbTiO3, the adsorption of small molecules within metal-organic frameworks (MOFs), the graphite/diamond phase transition, and the adsorption of an aromaticmolecule on the Ag(111) surface. Our results indicate that vdW-DF-cx is overall well suited to tackle these challenging systems. In addition to being a competitive density functional for sparse matter, the vdW-DF-cx construction presents a more robust general purpose functional that could be applied to a range of materials problems with a variety of competing interactions.

  10. Atomic imaging and modeling of H{sub 2}O{sub 2}(g) surface passivation, functionalization, and atomic layer deposition nucleation on the Ge(100) surface

    SciTech Connect (OSTI)

    Kaufman-Osborn, Tobin [Materials Science and Engineering Program, University of California, San Diego, La Jolla, California 92093 (United States); Chagarov, Evgueni A. [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093 (United States); Kummel, Andrew C., E-mail: akummel@ucsd.edu [Materials Science and Engineering Program, University of California, San Diego, La Jolla, California 92093 (United States); Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093 (United States)

    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 Ge–O–Al 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 Ge–O–Al monolayer to serve as an ideal template for further high-k deposition.

  11. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

    SciTech Connect (OSTI)

    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, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

  12. Tetrahalide Complexes of the [U(NR)(2)]2+ Ion: Synthesis, Theory, and Chlorine K-Edge X-ray Absorption Spectroscopy

    SciTech Connect (OSTI)

    Spencer, Liam P.; Yang, Ping; Minasian, Stefan G.; Jilek, Robert E.; Batista, Enrique R.; Boland, Kevin S.; Boncella, James M.; Conradson, S. D.; Clark, David L.; Hayton, Trevor W.; Kozimor, Stosh A.; Martin, Richard L.; MacInnes, Molly M.; Olson, Angela C.; Scott, Brian L.; Shuh, D. K.; Wilkerson, Marianne P.

    2013-02-13

    Synthetic routes to salts containing uranium bisimido tetrahalide anions [U(NR)(2)X-4](2-) (X = Cl-, Br-) and non-coordinating NEt4+ and PPh4+ countercations are reported. In general, these compounds can be prepared from U(NR)(2)I-2(THF)(x) (x = 2 and R = 'Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl-, the [U(NMe)(2)](2 +) cation also reacts with Br- to form stable [NEt4](2)[U(NMe)(2)Br-4] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO2](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh4](2)[U((NBu)-Bu-t)(2)Cl-4] and [PPh4](2)[UO2Cl4]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  13. Plate theory as the variational limit of the complementary energy functionals of inhomogeneous anisotropic linearly elastic bodies

    E-Print Network [OSTI]

    Francois Murat; Roberto Paroni

    2015-02-13

    We consider a sequence of linear hyper-elastic, inhomogeneous and fully anisotropic bodies in a reference configuration occupying a cylindrical region of height epsilon. We then study, by means of Gamma-convergence, the asymptotic behavior as epsilon goes to zero of the sequence of complementary energies. The limit functional is then identified as a dual problem for a two-dimensional plate. Our approach gives a direct characterization of the convergence of the equilibrating stress fields.

  14. Benchmarking the performance of density functional theory and point charge force fields in their description of sI methane hydrate against diffusion Monte Carlo

    SciTech Connect (OSTI)

    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 ; Alfè, 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.

  15. Differentiation of O-H and C-H Bond Scission Mechanisms of Ethylene Glycol on Pt and Ni/Pt Using Theory and Isotopic Labeling Experiments

    SciTech Connect (OSTI)

    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 O–H bond cleavage, followed by C–H and the second O–H bond cleavages, whereas on the Ni/Pt surface, both O–H 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.

  16. Application of the theory of Linear Singular Integral Equations and Contour Integration to Riemann Hilbert Problems for determination of new decoupled expressions of Chandrasekhar's X- and Y- functions for slab geometry in Radiative Transfer

    E-Print Network [OSTI]

    Rabindra Nath Das

    2007-02-22

    In Radiative transfer, the intensities of radiation from the bounding faces of finite slab are obtained in terms of X- and Y- functions of Chandrasekhar . Those are non linear non homogeneous coupled integral equations . Those non linear integral equations are meromorphically extended to the complex plane to get linear non homogeneous coupled integral equations. Those linear integral equations are converted to linear singular integral equations with. linear constraints . Those singular integral equations are then transformed to non homogeneous Riemann Hilbert Problems. Solutions of those Riemann Hilbert Problems are obtained using the theory of linear singular integral equations to decouple those X- and Y- functions. New forms of linear non homogeneous decoupled integral equations are derived for X- and Y- function separately with new linear constraints. Those new decoupled integral equations are transformed into linear singular integral equations to get two new separate non homogeneous Riemann Hilbert problems and to find solutions in terms of one known N- function and five new unknown functions in complex plane . All five functions are represented in terms of N-functions using the theory of contour integration >. Those X- and Y- functions are finally expressed in terms of that N - function and also in terms of H- functions of Chandrasekhar and of integrals in Cauchy principal value sense in the complex plane and real plane. both for conservative and non conservative cases . The H - functions for semi infinite atmosphere are derived as a limiting case from the expression of X- function of finite atmosphere.

  17. Systematic study of nuclear matrix elements in neutrinoless double-beta decay with a beyond mean-field covariant density functional theory

    E-Print Network [OSTI]

    J. M. Yao; L. S. Song; K. Hagino; P. Ring; J. Meng

    2015-01-29

    We report a systematic study of nuclear matrix elements (NMEs) in neutrinoless double-beta decays with a state-of-the-art beyond mean-field covariant density functional theory. The dynamic effects of particle-number and angular-momentum conservations as well as quadrupole shape fluctuations are taken into account with projections and generator coordinate method for both initial and final nuclei. The full relativistic transition operator is adopted to calculate the NMEs. The present systematic studies show that in most of the cases there is a much better agreement with the previous non-relativistic calculation based on the Gogny force than in the case of the nucleus $^{150}$Nd found in Song et al. [Phys. Rev. C 90, 054309 (2014)]. In particular, we find that the total NMEs can be well approximated by the pure axial-vector coupling term with a considerable reduction of the computational effort.

  18. Theoretical Spectroscopy Lectures Francesco Sottile, Valerie Veniard,

    E-Print Network [OSTI]

    Botti, Silvana

    -Dependent DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Francesco Green's functions-Dependent DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Francesco Green's functions-Dependent DFT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Francesco Green's functions

  19. Density functional theory studies on theelectronic, structural, phonon dynamicaland thermo-stability properties of bicarbonates MHCO3, M D Li, Na, K

    SciTech Connect (OSTI)

    Duan, Yuhua; Zhang, Bo; Sorescu, Dan C.; Johnson, Karl; Majzoub, Eric H; Luebke, David R.

    2012-07-01

    The structural, electronic, phonon dispersion and thermodynamic properties of MHCO3 (M D Li, Na, K) solids were investigated using density functional theory. The calculated bulk properties for both their ambient and the high-pressure phases are in good agreement with available experimental measurements. Solid phase LiHCO3 has not yet been observed experimentally. We have predicted several possible crystal structures for LiHCO3 using crystallographic database searching and prototype electrostatic ground state modeling. Our total energy and phonon free energy .FPH/ calculations predict that LiHCO3 will be stable under suitable conditions of temperature and partial pressures of CO2 and H2O. Our calculations indicate that the HCO􀀀 3 groups in LiHCO3 and NaHCO3 form an infinite chain structure through O#1; #1; #1;H#1; #1; #1;O hydrogen bonds. In contrast, the HCO􀀀 3 anions form dimers, .HCO􀀀 3 /2, connected through double hydrogen bonds in all phases of KHCO3. Based on density functional perturbation theory, the Born effective charge tensor of each atom type was obtained for all phases of the bicarbonates. Their phonon dispersions with the longitudinal optical–transverse optical splitting were also investigated. Based on lattice phonon dynamics study, the infrared spectra and the thermodynamic properties of these bicarbonates were obtained. Over the temperature range 0–900 K, the FPH and the entropies (S) of MHCO3 (M D Li, Na, K) systems vary as FPH.LiHCO3/ > FPH.NaHCO3/ > FPH.KHCO3/ and S.KHCO3/ > S.NaHCO3/ > S.LiHCO3/, respectively, in agreement with the available experimental data. Analysis of the predicted thermodynamics of the CO2 capture reactions indicates that the carbonate/bicarbonate transition reactions for Na and K could be used for CO2 capture technology, in agreement with experiments.

  20. Electronic states of thiophene/phenylene co-oligomers: Extreme-ultra violet excited photoelectron spectroscopy observations and density functional theory calculations

    SciTech Connect (OSTI)

    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.

  1. Simulating Ru L3-Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    SciTech Connect (OSTI)

    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.

  2. Experimental and DFT studies of initiation processes for butane isomerization over sulfated-zirconia catalysts

    SciTech Connect (OSTI)

    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.

  3. Chemisorption of (CHx and C2Hy) Hydrocarbons on Pt(111) Clusters and Surfaces from DFT Studies

    E-Print Network [OSTI]

    Goddard III, William A.

    Chemisorption of (CHx and C2Hy) Hydrocarbons on Pt(111) Clusters and Surfaces from DFT Studies Timo that these hydrocarbons all bind covalently (-bonds) to the surface, in agreement with the studies by Kua and Goddard on small Pt clusters. In nearly every case the structure of the adsorbed hydrocarbon achieves a saturated

  4. Double Field Theory on Group Manifolds (Thesis)

    E-Print Network [OSTI]

    Hassler, Falk

    2015-01-01

    This thesis deals with Double Field Theory (DFT), an effective field theory capturing the low energy dynamics of closed strings on a torus. It renders T-duality on a torus manifest by adding $D$ winding coordinates in addition to the $D$ space time coordinates. An essential consistency constraint of the theory, the strong constraint, only allows for field configurations which depend on half of the coordinates of the arising doubled space. I derive DFT${}_\\mathrm{WZW}$, a generalization of the current formalism. It captures the low energy dynamics of a closed bosonic string propagating on a compact group manifold. Its classical action and the corresponding gauge transformations arise from Closed String Field Theory up to cubic order in the massless fields. These results are rewritten in terms of a generalized metric and extended to all orders in the fields. There is an explicit distinction between background and fluctuations. For the gauge algebra to close, the latter have to fulfill a modified strong constrai...

  5. Reaction dynamics of OH{sup +}({sup 3}{sigma}{sup -})+C{sub 2}H{sub 2} studied with crossed beams and density functional theory calculations

    SciTech Connect (OSTI)

    Liu Li; Martin, Courtney; Farrar, James M. [Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)

    2006-10-07

    The reactions between OH{sup +}({sup 3}{sigma}{sup -}) and C{sub 2}H{sub 2} have been studied using crossed ion and molecular beams and density functional theory calculations. Both charge transfer and proton transfer channels are observed. Products formed by carbon-carbon bond cleavage analogous to those formed in the isoelectronic O({sup 3}P)+C{sub 2}H{sub 2} reaction, e.g., {sup 3}CH{sub 2}+HCO{sup +}, are not observed. The center of mass flux distributions of both product ions at three different energies are highly asymmetric, with maxima close to the velocity and direction of the precursor acetylene beam, characteristic of direct reactions. The internal energy distributions of the charge transfer products are independent of collision energy and are peaked at the reaction exothermicity, inconsistent with either the existence of favorable Franck-Condon factors or energy resonance. In proton transfer, almost the entire reaction exothermicity is transformed into product internal excitation, consistent with mixed energy release in which the proton is transferred with both the breaking and forming bonds extended. Most of the incremental translational energy in the two higher-energy experiments appears in product translational energy, providing an example of induced repulsive energy release.

  6. Dissociative adsorption of CH{sub 3}X (X = Br and Cl) on a silicon(100) surface revisited by density functional theory

    SciTech Connect (OSTI)

    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.

  7. Optimizing minimum free-energy crossing points in solution: Linear-response free energy/spin-flip density functional theory approach

    SciTech Connect (OSTI)

    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.

  8. Calculation of properties of crystalline lithium hydride using correlated wave function theory S. J. Nolan,1 M. J. Gillan,2,3 D. Alf,2,3,4 N. L. Allan,1 and F. R. Manby1

    E-Print Network [OSTI]

    Alfè, Dario

    Calculation of properties of crystalline lithium hydride using correlated wave function theory S. J, and cohesive energy of lithium hydride are calculated to very high accuracy through a combination of periodic. All calculated properties of lithium hydride and deuteride agree with empirical observations to within

  9. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    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 (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.« less

  10. Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

    SciTech Connect (OSTI)

    Al-Hamdani, Yasmine S.; Michaelides, Angelos; Alfè, 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.

  11. X-ray diffraction, spectroscopic and DFT studies of 1-(4-bromophenyl)-3,5-diphenylformazan

    SciTech Connect (OSTI)

    Tezcan, H.; Tokay, N.; Alpaslan, G.; Erdönmez, 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) Å, 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.

  12. DFT modeling of adsorption onto uranium metal using large-scale parallel computing

    SciTech Connect (OSTI)

    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)

  13. Structure, stability, and electronic property of carbon-doped gold clusters Au{sub n}C{sup ?} (n = 1–10): A density functional theory study

    SciTech Connect (OSTI)

    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 = 1–10) 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.

  14. Spectral Functions in QFT

    E-Print Network [OSTI]

    Pablo Pisani

    2015-05-16

    We present a pedagogical exposition of some applications of functional methods in quantum field theory: we use heat-kernel and zeta-function techniques to study the Casimir effect, the pair production in strong electric fields, quantum fields at finite temperature and beta-functions for a self-interacting scalar field, QED and pure Yang-Mills theories. The more recent application to the UV/IR mixing phenomenon in noncommutative theories is also discussed in this framework.

  15. Interfacial Properties and Design of Functional Energy Materials

    SciTech Connect (OSTI)

    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.

  16. Screened Hybrid and DFT + U Studies of the Structural, Electronic, and Optical Properties of U3O8

    SciTech Connect (OSTI)

    Wen, Xiaodong; Martin, Richard L.; Scuseria, Gustavo E.; Rudin, Sven P.; Batista, Enrique R.; Burrell, Anthony K.

    2012-11-26

    A systematic comparison of the structures and electronic and optical properties of U3O8 in the c2mm, P¯62m, and P21/m structures (the ?, ?, and ? phases, respectively) is performed using density functional theory + U (PBE + U) and the Heyd–Scuseria–Ernzerhof screened hybrid functional (HSE). The relationship between the semiconducting C2mm phase of U3O8 and the high temperature, metallic P¯62m phase is explored in more detail. Our calculated results show that the HSE functional gives a better description of the electronic and optical properties when compared with available experimental data for the ? and ? phases, but neither approach does particularly well for the high pressure ? phase.

  17. Efficient Pulse-Doppler Processing and Ambiguity Functions of Nonuniform Coherent Pulse Trains

    E-Print Network [OSTI]

    Nehorai, Arye

    Efficient Pulse-Doppler Processing and Ambiguity Functions of Nonuniform Coherent Pulse Trains Lafayette, Indiana 47907 Email: {srasool, mrb}@purdue.edu Abstract--We propose a DFT based pulse Doppler processing receiver for staggered pulse trains. The proposed receiver is a simple extension of traditional

  18. First-Principles Studies of Photoinduced Charge Transfer in Noncovalently Functionalized Carbon Nanotubes

    E-Print Network [OSTI]

    Chu, Iek-Heng; Cheng, Hai-Ping

    2013-01-01

    We have studied the energetics, electronic structure, optical excitation, and electron relaxation of dinitromethane molecules (CH$_{2}$N$_{2}$O$_{4}$) adsorbed on semiconducting carbon nanotubes (CNTs) of chiral index (n,0) (n=7, 10, 13, 16, 19). Using first-principles density functional theory (DFT) with generalized gradient approximations and van der Waals corrections, we have calculated adsorption energies of dinitropentylpyrene, in which the dinitromethane is linked to the pyrene via an aliphatic chain, on a CNT. A 75.26 kJ/mol binding energy has been found, which explains why such aliphatic chain-pyrene units can be and have been used in experiments to bind functional molecules to CNTs. The calculated electronic structures show that the dinitromethane introduces a localized state inside the band gap of CNT systems of n=10, 13, 16 and 19; such a state can trap an electron when the CNT is photoexcited. We have therefore investigated the dynamics of intra-band relaxations using the reduced density matrix fo...

  19. First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels

    SciTech Connect (OSTI)

    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.

  20. p-ADIC ARAKELOV THEORY: LOCAL THEORY

    E-Print Network [OSTI]

    " on the completions above p. In this part of the paper we only deal with the local theory, i.e., above p. This really, on a complete curve over a p-adic #12;eld. The goal of the local theory is to describe an extension of this pairing, by giving a Green function G(P; Q) with certain desirable properties, in such a way that (1.1) DX

  1. 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 = (?, ?, ?), 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

  2. Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.

    SciTech Connect (OSTI)

    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.

  3. p-ADIC ARAKELOV THEORY: LOCAL THEORY

    E-Print Network [OSTI]

    involving "Coleman analysis" on the completions above p. In this part of the paper we only deal. The goal of the local theory is to describe an exten* *sion of this pairing, by giving a Green function G (1.1) niPi, mjQj = nimjG(Pi, Qj) To isolate a canonical as possible Green

  4. Two-component multi-configurational second-order perturbation theory with Kramers restricted complete active space self-consistent field reference function and spin-orbit relativistic effective core potential

    SciTech Connect (OSTI)

    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.

  5. Structural, thermodynamic and optical properties of MgF{sub 2} studied from first-principles theory

    SciTech Connect (OSTI)

    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.

  6. Study of the effect of semi-infinite crystalline electrodes on transmission of gold atomic wires using DFT

    E-Print Network [OSTI]

    Sattar, Abdul; Yasmeen, Sumaira; Javed, Hafsa; Latif, Hamid; Mahmood, Hasan; Iqbal, Azmat; Usman, Arslan; Akhtar, Majid Niaz; Khan, Salman Naeem; Dousti, M R

    2015-01-01

    First principle calculations of the conductance of gold wires containing 3-8 atoms each with 2.39 {\\AA} bond length were performed using density functional theory. Three different configuration of wire/electrodes were used. For zigzag wire with semi-infinite crystalline electrodes, even-odd oscillation is observed which is consistent with the previously reported results. A lower conductance was observed for the chain in semi-infinite crystalline electrodes compared to the chains suspended in wire-like electrode. The calculated transmission spectrum for the straight and zig-zag wires suspended between semi-infinite crystalline electrodes showed suppression of transmission channels due to electron scattering occurring at the electrode-wire interface.

  7. Linear response theory in the continuum for deformed nuclei: Green's function vs. time-dependent Hartree-Fock with the absorbing-boundary condition

    E-Print Network [OSTI]

    Takashi Nakatsukasa; Kazuhiro Yabana

    2004-12-05

    The continuum random-phase approximation is extended to the one applicable to deformed nuclei. We propose two different approaches. One is based on the use of the three dimensional (3D) Green's function and the other is the small-amplitude TDHF with the absorbing-boundary condition. Both methods are based on the 3D Cartesian grid representation and applicable to systems without any symmetry on nuclear shape. The accuracy and identity of these two methods are examined with the BKN interaction. Using the full Skyrme energy functional in the small-amplitude TDHF approach, we study the isovector giant dipole states in the continuum for O-16 and for even-even Be isotopes.

  8. Published: April 05, 2011 r 2011 American Chemical Society 1296 dx.doi.org/10.1021/ct100607w |J. Chem. Theory Comput. 2011, 7, 12961306

    E-Print Network [OSTI]

    Herbert, John

    -Functional Description of the 1 La State in Polycyclic Aromatic Hydrocarbons: Charge-Transfer Character in Disguise? Ryan aromatic hydrocarbons (PAHs) includes two singlet excited states that are often denoted 1 La and 1 Lb. Time operator into short- and long-range components.8,15,21À23 While conventional TD-DFT's propensity

  9. Finite quantum gauge theories

    E-Print Network [OSTI]

    Modesto, Leonardo; Rachwal, Leslaw

    2015-01-01

    We explicitly compute the one-loop exact beta function for a nonlocal extension of the standard gauge theory, in particular Yang-Mills and QED. The theory, made of a weakly nonlocal kinetic term and a local potential of the gauge field, is unitary (ghost-free) and perturbatively super-renormalizable. Moreover, in the action we can always choose the potential (consisting of one "killer operator") to make zero the beta function of running gauge coupling constant. The outcome is "a UV finite theory for any gauge interaction". Our calculations are done in D=4, but the results can be generalized to even or odd spacetime dimensions. We compute the contribution to the beta function from two different killer operators by using two independent techniques, namely the Feynman diagrams and the Barvinsky-Vilkovisky traces. By making the theories finite we are able to solve also the Landau pole problems, in particular in QED. Without any potential the beta function of the one-loop super-renormalizable theory shows a univer...

  10. Finite quantum gauge theories

    E-Print Network [OSTI]

    Leonardo Modesto; Marco Piva; Leslaw Rachwal

    2015-06-20

    We explicitly compute the one-loop exact beta function for a nonlocal extension of the standard gauge theory, in particular Yang-Mills and QED. The theory, made of a weakly nonlocal kinetic term and a local potential of the gauge field, is unitary (ghost-free) and perturbatively super-renormalizable. Moreover, in the action we can always choose the potential (consisting of one "killer operator") to make zero the beta function of running gauge coupling constant. The outcome is "a UV finite theory for any gauge interaction". Our calculations are done in D=4, but the results can be generalized to even or odd spacetime dimensions. We compute the contribution to the beta function from two different killer operators by using two independent techniques, namely the Feynman diagrams and the Barvinsky-Vilkovisky traces. By making the theories finite we are able to solve also the Landau pole problems, in particular in QED. Without any potential the beta function of the one-loop super-renormalizable theory shows a universal Landau pole in the running coupling constant in the ultraviolet regime (UV), regardless of the specific higher-derivative structure. However, the dressed propagator shows neither the Landau pole in the UV, nor the singularities in the infrared regime (IR).

  11. Accurate nuclear masses from a three parameter Kohn-Sham DFT approach (BCPM)

    SciTech Connect (OSTI)

    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.

  12. Bond length and electric current oscillation of long linear carbon chains: Density functional theory, MpB model, and quantum spin transport studies

    SciTech Connect (OSTI)

    Oeiras, R. Y.; Silva, E. Z. da [Institute of Physics “Gleb Wataghin”, University of Campinas-Unicamp, 13083-859 Campinas, SP (Brazil)] [Institute of Physics “Gleb Wataghin”, University of Campinas-Unicamp, 13083-859 Campinas, SP (Brazil)

    2014-04-07

    Carbon linear atomic chains attached to graphene have experimentally been produced. Motivated by these results, we study the nature of the carbon bonds in these nanowires and how it affects their electrical properties. In the present study we investigate chains with different numbers of atoms and we observe that nanowires with odd number of atoms present a distinct behavior than the ones with even numbers. Using graphene nanoribbons as leads, we identify differences in the quantum transport of the chains with the consequence that even and odd numbered chains have low and high electrical conduction, respectively. We also noted a dependence of current with the wire size. We study this unexpected behavior using a combination of first principles calculations and simple models based on chemical bond theory. From our studies, the electrons of carbon nanowires present a quasi-free electron behavior and this explains qualitatively the high electrical conduction and the bond lengths with unexpected values for the case of odd nanowires. Our study also allows the understanding of the electric conduction dependence with the number of atoms and their parity in the chain. In the case of odd number chains a proposed ?-bond (MpB) model describes unsaturated carbons that introduce a mobile ?-bond that changes dramatically the structure and transport properties of these wires. Our results indicate that the nature of bonds plays the main role in the oscillation of quantum electrical conduction for chains with even and odd number of atoms and also that nanowires bonded to graphene nanoribbons behave as a quasi-free electron system, suggesting that this behavior is general and it could also remain if the chains are bonded to other materials.

  13. Electronic and thermoelectric properties of Ce{sub 3}Te{sub 4} and La{sub 3}Te{sub 4} computed with density functional theory with on-site Coulomb interaction correction

    SciTech Connect (OSTI)

    Vo, Trinh; Allmen, Paul von; Huang, Chen-Kuo; Ma, James; Bux, Sabah; Fleurial, Jean-Pierre [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California 91109 (United States)

    2014-10-07

    The electronic properties and Seebeck coefficients of Ce{sub 3}Te{sub 4} and La{sub 3}Te{sub 4} are computed using Density Functional Theory with on-site Coulomb interaction correction. We found that the Seebeck coefficients of Ce{sub 3}Te{sub 4} and La{sub 3}Te{sub 4} are almost equal at temperatures larger than the Curie temperature of Ce{sub 3}Te{sub 4}, and in good agreement with the measurements reported by May et al. [Phys. Rev. B 86, 035135 (2012)]. At temperatures below the Curie temperature, the Seebeck coefficient of Ce{sub 3}Te{sub 4} increases due to the ferromagnetic ordering, which leads the f-electron of Ce to contribute to the Seebeck coefficient in the relevant range of electron concentration.

  14. Constructive Matrix Theory

    E-Print Network [OSTI]

    V. Rivasseau

    2007-06-08

    We extend the technique of constructive expansions to compute the connected functions of matrix models in a uniform way as the size of the matrix increases. This provides the main missing ingredient for a non-perturbative construction of the $\\phi^{\\star 4}_4$ field theory on the Moyal four dimensional space.

  15. DFT+U Study of Polaronic Conduction in Li2O2 and Li2CO3: Implications for Li-Air Batteries

    E-Print Network [OSTI]

    Thygesen, Kristian

    DFT+U Study of Polaronic Conduction in Li2O2 and Li2CO3: Implications for Li-Air Batteries J. M-air batteries are known to be Li2O2 and residual Li2CO3. Recent experiments indicate that the charge transport through these materials is the main limiting factor for the battery performance. It has been also shown

  16. Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

    SciTech Connect (OSTI)

    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.

  17. Discontinuous Lyapunov Functions for Nonasymptotic Stability Analysis

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    Discontinuous Lyapunov Functions for Nonasymptotic Stability Analysis A. Polyakov Inria Lille of discontinuous control systems using discontinuous Lyapunov functions. Elements of Filippov theory of generalized derivatives and non-smooth Lyapunov functions are considered. The generalized Lyapunov theorems

  18. Graph Theory

    SciTech Connect (OSTI)

    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.

  19. Understanding oxygen adsorption on 9.375 at. % Ga-stabilized ?-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 ?-phase lattice may also provide resistance against corrosion/oxidation of plutonium. In this paper, we modeled a 9.375 at. % Ga stabilized ?-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

  20. A COMPLEXITY THEORY OF CONSTRUCTIBLE FUNCTIONS AND ...

    E-Print Network [OSTI]

    2014-09-30

    sheaf-theoretic variant of the real quantifier elimination problem. We pose the .... lower bound on the complexity on the partition of the Hardt's triviality theorem.

  1. Functional Keldysh theory of spin torques 

    E-Print Network [OSTI]

    Duine, R. A.; Nunez, A. S.; Sinova, Jairo; MacDonald, A. H.

    2007-01-01

    spintronic materials, in par- ticular, we will argue that orbitals which have dominant d character contribute more strongly to the magnetization than to transport and that ? will tend to be larger than ? as a consequence. In this paper, we present a...

  2. The bonding, charge distribution, spin ordering, optical, and elastic properties of four MAX phases Cr{sub 2}AX (A?=?Al or Ge, X?=?C or N): From density functional theory study

    SciTech Connect (OSTI)

    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 (?), 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 ?.

  3. Conjugate flow action functionals

    E-Print Network [OSTI]

    Daniele Venturi

    2013-10-15

    We present a new general method to construct an action functional for a non-potential field theory. The key idea relies on representing the governing equations of the theory relative to a diffeomorphic flow of curvilinear coordinates which is assumed to be functionally dependent on the solution field. Such flow, which will be called the conjugate flow of the theory, evolves in space and time similarly to a physical fluid flow of classical mechanics and it can be selected in order to symmetrize the Gateaux derivative of the field equations with respect to suitable local bilinear forms. This is equivalent to requiring that the governing equations of the field theory can be derived from a principle of stationary action on a Lie group manifold. By using a general operator framework, we obtain the determining equations of such manifold and the corresponding conjugate flow action functional. In particular, we study scalar and vector field theories governed by second-order nonlinear partial differential equations. The identification of transformation groups leaving the conjugate flow action functional invariant could lead to the discovery of new conservation laws in fluid dynamics and other disciplines.

  4. p-ADIC ARAKELOV THEORY AMNON BESSER

    E-Print Network [OSTI]

    of Colmez* * on p-adic Green functions. We introduce the p-adic version of a metrized l* *ine analy- sis" [CdS88 , Col98, Bes02a] on the completions above p. This "local" part of t* *he theory. The goal of the local theory is to describe an exten* *sion of this pairing, by giving a Green function G

  5. Star products on graded manifolds and $?'$-corrections to double field theory

    E-Print Network [OSTI]

    Andreas Deser

    2015-11-12

    Originally proposed as an $O(d,d)$-invariant formulation of classical closed string theory, double field theory (DFT) offers a rich source of mathematical structures. Most prominently, its gauge algebra is determined by the so-called C-bracket, a generalization of the Courant bracket of generalized geometry, in the sense that it reduces to the latter by restricting the theory to solutions of a "strong constraint". Recently, infinitesimal deformations of these structures in the string sigma model coupling $\\alpha'$ were found. In this short contribution, we review constructing the Drinfel'd double of a Lie bialgebroid and offer how this can be applied to reproduce the C-bracket of DFT in terms of Poisson brackets. As a consequence, we are able to explain the $\\alpha'$-deformations via a graded version of the Moyal-Weyl product in a class of examples. We conclude with comments on the relation between $B$- and $\\beta$-transformations in generalized geometry and the Atiyah algebra on the Drinfel'd double.

  6. MiniDFT

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    the Fock matrix, Fast Fourier Transforms are used to tranform orbitals from the plane wave basis ( where the kinetic energy is most readily compted ) to real space (where the...

  7. Arithmetical Functions : Infinite Products

    E-Print Network [OSTI]

    Garimella Rama Murthy

    2012-11-26

    In this technical report, certain interesting classification of arithmetical functions is proposed. The notion of additively decomposable and multiplicatively decomposable arithmetical functions is proposed. The concepts of arithmetical polynomials and arithmetical power series are introduced. Using these concepts, an interesting Theorem relating arithmetical power series and infinite products has been proved. Also arithmetical polynomials are related to probabilistic number theory. Furthermore some results related to the Waring problem are discussed.

  8. Holographic Quenches and Fermionic Spectral Functions

    E-Print Network [OSTI]

    N. Callebaut; B. Craps; F. Galli; D. C. Thompson; J. Vanhoof; J. Zaanen; Hongbao Zhang

    2014-11-04

    Using holographic methods we investigate the behaviour of fermionic spectral functions of strongly coupled 2+1 dimensional field theories as both temperature and chemical potential are quenched.

  9. Riemann zeta function and quantum chaos

    E-Print Network [OSTI]

    Eugene Bogomolny

    2007-08-30

    A brief review of recent developments in the theory of the Riemann zeta function inspired by ideas and methods of quantum chaos is given.

  10. Building a Universal Nuclear Energy Density Functional

    SciTech Connect (OSTI)

    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.

  11. Theta-functions on noncommutative tori

    E-Print Network [OSTI]

    Albert Schwarz

    2001-07-25

    Ordinary theta-functions can be considered as holomorphic sections of line bundles over tori. We show that one can define generalized theta-functions as holomorphic elements of projective modules over noncommutative tori (theta-vectors). The theory of these new objects is not only more general, but also much simpler than the theory of ordinary theta-functions. It seems that the theory of theta-vectors should be closely related to Manin's theory of quantized theta-functions, but we don't analyze this relation.

  12. Quantum Field Theory of Fluids

    E-Print Network [OSTI]

    Ben Gripaios; Dave Sutherland

    2015-04-23

    The quantum theory of fields is largely based on studying perturbations around non-interacting, or free, field theories, which correspond to a collection of quantum-mechanical harmonic oscillators. The quantum theory of an ordinary fluid is `freer', in the sense that the non-interacting theory also contains an infinite collection of quantum-mechanical free particles, corresponding to vortex modes. By computing a variety of correlation functions at tree- and loop-level, we give evidence that a quantum perfect fluid can be consistently formulated as a low-energy, effective field theory. We speculate that the quantum behaviour is radically different to both classical fluids and quantum fields, with interesting physical consequences for fluids in the low temperature regime.

  13. Symplectic quantum mechanics and Chern-Simons gauge theory. I

    SciTech Connect (OSTI)

    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.

  14. A first-principles density functional theory study of the electronic structural and thermodynamic properties of M2ZrO3 and M2CO3 (M=Na, K) and their capabilities for CO2 capture

    SciTech Connect (OSTI)

    Yuhua Duan

    2012-01-01

    Alkali metal zirconates could be used as solid sorbents for CO{sub 2} capture. The structural, electronic, and phonon properties of Na{sub 2}ZrO{sub 3}, K{sub 2}ZrO{sub 3}, Na{sub 2}CO{sub 3}, and K{sub 2}CO{sub 3} are investigated by combining the density functional theory with lattice phonon dynamics. The thermodynamics of CO{sub 2} absorption/desorption reactions of these two zirconates are analyzed. The calculated results show that their optimized structures are in a good agreement with experimental measurements. The calculated band gaps are 4.339 eV (indirect), 3.641 eV (direct), 3.935 eV (indirect), and 3.697 eV (direct) for Na{sub 2}ZrO{sub 3}, K{sub 2}ZrO{sub 3}, Na{sub 2}CO{sub 3}, and K{sub 2}CO{sub 3}, respectively.The calculated phonon dispersions and phonon density of states for M{sub 2}ZrO{sub 3} and M{sub 2}CO{sub 3} (M = K, Na, Li) revealed that from K to Na to Li, their frequency peaks are shifted to high frequencies due to the molecular weight decreased from K to Li. From the calculated reaction heats and relationships of free energy change versus temperatures and CO{sub 2} pressures of the M{sub 2}ZrO{sub 3} (M = K, Na, Li) reacting with CO{sub 2}, we found that the performance of Na{sub 2}ZrO{sub 3} capturing CO{sub 2} is similar to that of Li{sub 2}ZrO{sub 3} and is better than that of K{sub 2}ZrO{sub 3}. Therefore, Na{sub 2}ZrO{sub 3} and Li{sub 2}ZrO{sub 3} are good candidates of high temperature CO{sub 2} sorbents and could be used for post combustion CO{sub 2} capture technologies.

  15. Salinas : theory manual.

    SciTech Connect (OSTI)

    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.

  16. Quiver gauge theories and integrable lattice models

    E-Print Network [OSTI]

    Junya Yagi

    2015-06-30

    We discuss connections between certain classes of supersymmetric quiver gauge theories and integrable lattice models from the point of view of topological quantum field theories (TQFTs). The relevant classes include 4d $\\mathcal{N} = 1$ theories known as brane box and brane tilling models, 3d $\\mathcal{N} = 2$ and 2d $\\mathcal{N} = (2,2)$ theories obtained from them by compactification, and 2d $\\mathcal{N} = (0,2)$ theories closely related to these theories. We argue that their supersymmetric indices carry structures of TQFTs equipped with line operators, and as a consequence, are equal to the partition functions of lattice models. The integrability of these models follows from the existence of extra dimension in the TQFTs, which emerges after the theories are embedded in M-theory. The Yang-Baxter equation expresses the invariance of supersymmetric indices under Seiberg duality and its lower-dimensional analogs.

  17. The Differential Approach to Superlative Index Number Theory

    E-Print Network [OSTI]

    Barnett, William A.; Choi, Ki-Hong; Sinclair, Tara M.

    2003-09-01

    Diewert’s “superlative” index numbers, defined to be exact for second-order aggregator functions, unify index number theory with aggregation theory but have been difficult to identify. We present a new approach to finding ...

  18. Wave function derivation of the JIMWLK equation

    E-Print Network [OSTI]

    Alexey V. Popov

    2008-12-16

    Using the stationary lightcone perturbation theory, we propose the complete and careful derivation the JIMWLK equation. We show that the rigorous treatment requires the knowledge of a boosted wave function with second order accuracy. Previous wave function approaches are incomplete and implicitly used the time ordered perturbation theory, which requires a usage of an external target field.

  19. Lithium Local Pseudopotential Using

    E-Print Network [OSTI]

    Petta, Jason

    Lithium Local Pseudopotential Using DFT Sergio Orozco Student Advisor: Chen Huang Faculty Mentor Lithium LPS Test Lithium LPS #12;Density Functional Theory (DFT) Successful quantum mechanical approach (1979) #12;Building LPS for Lithium Create a LPS using NLPS density for Lithium Test LPS by comparing

  20. Tactics for male reproductive success in plants: contrasting insights of sex allocation theory and pollen presentation theory

    E-Print Network [OSTI]

    Thomson, James D.

    allocation theory is that an organism's reproductive success, through either male or female function, can in that function. The shapes of these curves determine what patterns of resource allocation can be evolutionarily and female function. Sex allocation theory matured rapidly through the efforts of Charnov 55(1979, 1982

  1. De Branges spaces and Krein's theory of entire operators

    E-Print Network [OSTI]

    Luis O. Silva; Julio H. Toloza

    2015-06-23

    This work presents a contemporary treatment of Krein's entire operators with deficiency indices $(1,1)$ and de Branges' Hilbert spaces of entire functions. Each of these theories played a central role in the research of both renown mathematicians. Remarkably, entire operators and de Branges spaces are intimately connected and the interplay between them has had an impact in both spectral theory and the theory of functions. This work exhibits the interrelation between Krein's and de Branges' theories by means of a functional model and discusses recent developments, giving illustrations of the main objects and applications to the spectral theory of difference and differential operators.

  2. Quantum theory of light double-slit diffraction

    E-Print Network [OSTI]

    Xiang-Yao Wu; Hong Li; Bo-Jun Zhang; Ji Ma; Xiao-Jing Liu; Nuo Ba; He Dong; Si-Qi Zhang; Jing Wang; Yi-Heng Wu; Xin-Guo Yin

    2013-05-10

    In this paper, we study the light double-slit diffraction experiment with quantum theory approach. Firstly, we calculate the light wave function in slits by quantum theory of photon. Secondly, we calculate the diffraction wave function with Kirchhoff's law. Thirdly, we give the diffraction intensity of light double-slit diffraction, which is proportional to the square of diffraction wave function. Finally, we compare calculation result of quantum theory and classical electromagnetic theory with the experimental data. We find the quantum calculate result is accordance with the experiment data, and the classical calculation result with certain deviation. So, the quantum theory is more accurately approach for studying light diffraction.

  3. Computer Stochastics in Scalar Quantum Field Theory

    E-Print Network [OSTI]

    C. B. Lang

    1993-12-01

    This is a series of lectures on Monte Carlo results on the non-perturbative, lattice formulation approach to quantum field theory. Emphasis is put on 4D scalar quantum field theory. I discuss real space renormalization group, fixed point properties and logarithmic corrections, partition function zeroes, the triviality bound on the Higgs mass, finite size effects, Goldstone bosons and chiral perturbation theory, and the determination of scattering phase shifts for some scalar models.

  4. Pizza into Java: Translating theory into practice

    E-Print Network [OSTI]

    Wadler, Philip

    Pizza into Java: Translating theory, Pizza is a strict superset of Java that incorporatesothreehigher-order function* *s, and ideas from.algebraic data types. Pizza is defined by translation into Java andPcompilesiintozza attempts to make

  5. Control of a highly flexible rotating beam: theory and experiments 

    E-Print Network [OSTI]

    Chang, Pei-Ming

    1990-01-01

    state of art control methodologies that include (i) classical proportional plus derivative (PD) control (ii) Linear Quadratic Regulator (LQR) (iii) servomechanism theory (iv) Lyapunov theory and (v) quantitative feedback theory (QFT), (3... Functions CHAPTER III . CONTROL THEORY 6 7 7 10 15 16 17 25 27 3. 1 Collocated PD Control 3. 2 Linear State Feedback Control 3. 3 Robust Servo-Mechanism Theory 3. 4 Robust Control Synthesized by Lyapunov's Second Method 3. 5 Quantitative...

  6. Effective Field Theory for Top Quark Physics

    E-Print Network [OSTI]

    Cen Zhang; Scott Willenbrock

    2010-08-18

    Physics beyond the standard model can affect top-quark physics indirectly. We describe the effective field theory approach to describing such physics, and contrast it with the vertex-function approach that has been pursued previously. We argue that the effective field theory approach has many fundamental advantages and is also simpler.

  7. Block theory Fusion systems

    E-Print Network [OSTI]

    Block theory Fusion systems Results Block theory and fusion systems Benjamin Sambale Jena 02. 05. 2011 Benjamin Sambale Block theory and fusion systems #12;Block theory Fusion systems Results Blocks closed field of characteristic p. Benjamin Sambale Block theory and fusion systems #12;Block theory

  8. Origin of anomalous atomic vibrations in efficient thermoelectrics...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    of S(Q,E) measured with INS (left) and calculated (right) with density functional theory (DFT). SnTe results are the top and PbTe results at the bottom. White arrows point...

  9. A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water

    E-Print Network [OSTI]

    Wang, Lee-Ping

    We present a quantum mechanical/molecular mechanical (QM/MM) explicit solvent model for the computation of standard reduction potentials E[subscript 0]. The QM/MM model uses density functional theory (DFT) to model the ...

  10. Structures and Reactivity of Transition-Metal Compounds Featuring Metal-Ligand Multiple Bonds 

    E-Print Network [OSTI]

    Xu, Zhenggang

    2014-07-25

    This dissertation presents the results from density functional theory (DFT) calculations on three major projects I have been working on over the past several years. The first system is focused on the structure and reactivity ...

  11. Theoretical Studies of Structures and Mechanisms in Organometallic and Bioinorganic Chemistry: Heck Reaction with Palladium Phosphines, Active Sites of Superoxide Reductase and Cytochrome P450 Monooxygenase, and Tetrairon Hexathiolate Hydrogenase Model 

    E-Print Network [OSTI]

    Surawatanawong, Panida

    2010-07-14

    The electronic structures and reaction mechanisms of transition-metal complexes can be calculated accurately by density functional theory (DFT) in cooperation with the continuum solvation model. The palladium catalyzed ...

  12. A theoretical analysis of interstitial hydrogen : pressure-composition-temperature, chemical potential, enthalpy and entropy

    E-Print Network [OSTI]

    Orondo, Peter Omondi

    2012-01-01

    We provide a first principles analysis of the physics and thermodynamics of interstitial hydrogen in metal. By utilizing recent advances in Density Functional Theory (DFT) to get state energies of the metal-hydrogen system, ...

  13. Elucidating Nucleation and Growth Behavior of Single-Walled Carbon Nanotubes obtained via Catalyzed Synthesis 

    E-Print Network [OSTI]

    Burgos Beltran, Juan Carlos

    2014-11-07

    The catalytic growth of single-walled carbon nanotubes (SWCNTs) is studied using reactive molecular dynamics (RMD) simulations and density functional theory (DFT) calculations. Computational calculations are performed in order to achieve a better...

  14. Vibrational Spectra, Theoretical Calculations, and Structures of Cyclic Silanes, 2,4,7-Trioxa(3.3.0)Octane and Botryococcenes 

    E-Print Network [OSTI]

    Chun, Hye Jin

    2014-12-08

    The vibrational spectra and structures of several cyclic silanes and a bicyclic molecule have been investigated with high-level ab initio and density function theory (DFT) calculations. In addition, the Raman spectra of botryococcene hydrocarbons...

  15. Understanding mechanisms for C-H bond activation 

    E-Print Network [OSTI]

    Vastine, Benjamin Alan

    2009-05-15

    The results from density functional theory (DFT) studies into C–H bond activation, hydrogen transfer, and alkyne–to–vinylidene isomerization are presented in this work. The reaction mechanism for the reductive elimination ...

  16. Green's Functions in Perturbative Quantum Gravity

    E-Print Network [OSTI]

    Sudhaker Upadhyay; Bhabani Prasad Mandal

    2015-04-03

    We show that the Green's functions in non-linear gauge in the theory of perturbative quantum gravity is expressed as a series in terms of those in linear gauges. This formulation is also holds for operator Green's functions. We further derive the explicit relation between the Green's functions in the theory of perturbative quantum gravity in a pair of arbitary gauges. This process involves some sort of modified FFBRST transformations which is derivable from infinitesimal field-dependent BRST transformations.

  17. Time functions as utilities

    E-Print Network [OSTI]

    E. Minguzzi

    2009-09-04

    Every time function on spacetime gives a (continuous) total preordering of the spacetime events which respects the notion of causal precedence. The problem of the existence of a (semi-)time function on spacetime and the problem of recovering the causal structure starting from the set of time functions are studied. It is pointed out that these problems have an analog in the field of microeconomics known as utility theory. In a chronological spacetime the semi-time functions correspond to the utilities for the chronological relation, while in a K-causal (stably causal) spacetime the time functions correspond to the utilities for the K^+ relation (Seifert's relation). By exploiting this analogy, we are able to import some mathematical results, most notably Peleg's and Levin's theorems, to the spacetime framework. As a consequence, we prove that a K-causal (i.e. stably causal) spacetime admits a time function and that the time or temporal functions can be used to recover the K^+ (or Seifert) relation which indeed turns out to be the intersection of the time or temporal orderings. This result tells us in which circumstances it is possible to recover the chronological or causal relation starting from the set of time or temporal functions allowed by the spacetime. Moreover, it is proved that a chronological spacetime in which the closure of the causal relation is transitive (for instance a reflective spacetime) admits a semi-time function. Along the way a new proof avoiding smoothing techniques is given that the existence of a time function implies stable causality, and a new short proof of the equivalence between K-causality and stable causality is given which takes advantage of Levin's theorem and smoothing techniques.

  18. Group field theories generating polyhedral complexes

    E-Print Network [OSTI]

    Johannes Thürigen

    2015-06-28

    Group field theories are a generalization of matrix models which provide both a second quantized reformulation of loop quantum gravity as well as generating functions for spin foam models. While states in canonical loop quantum gravity, in the traditional continuum setting, are based on graphs with vertices of arbitrary valence, group field theories have been defined so far in a simplicial setting such that states have support only on graphs of fixed valency. This has led to the question whether group field theory can indeed cover the whole state space of loop quantum gravity. In this contribution based on [1] I present two new classes of group field theories which satisfy this objective: i) a straightforward, but rather formal generalization to multiple fields, one for each valency and ii) a simplicial group field theory which effectively covers the larger state space through a dual weighting, a technique common in matrix and tensor models. To this end I will further discuss in some detail the combinatorial structure of the complexes generated by the group field theory partition function. The new group field theories do not only strengthen the links between the mentioned quantum gravity approaches but, broadening the theory space of group field theories, they might also prove useful in the investigation of renormalizability.

  19. Random wave functions and percolation

    E-Print Network [OSTI]

    E. Bogomolny; C. Schmit

    2007-08-31

    Recently it was conjectured that nodal domains of random wave functions are adequately described by critical percolation theory. In this paper we strengthen this conjecture in two respects. First, we show that, though wave function correlations decay slowly, a careful use of Harris' criterion confirms that these correlations are unessential and nodal domains of random wave functions belong to the same universality class as non critical percolation. Second, we argue that level domains of random wave functions are described by the non-critical percolation model.

  20. Gauge Dressing of 2D Field Theories

    E-Print Network [OSTI]

    Ian I. Kogan; Alex Lewis; Oleg A. Soloviev

    1996-07-05

    By using the gauge Ward identities, we study correlation functions of gauged WZNW models. We show that the gauge dressing of the correlation functions can be taken into account as a solution of the Knizhnik-Zamolodchikov equation. Our method is analogous to the analysis of the gravitational dressing of 2D field theories.

  1. Introduction to Control & Optimal control theory Maria Soledad Aronna

    E-Print Network [OSTI]

    Moreira, Carlos Gustavo

    Introduction to Control & Optimal control theory Mar´ia Soledad Aronna IMPA, Estrada Dona Castorina 110, 22460-320 Rio de Janeiro - RJ, Brazil November 17, 2014 Control theory deals with ordinary interval of time. Optimal control theory studies situations in which one associates a cost functional

  2. Composite Photon Theory Versus Elementary Photon Theory

    E-Print Network [OSTI]

    Walton A. Perkins

    2015-03-02

    The purpose of this paper is to show that the composite photon theory measures up well against the Standard Model's elementary photon theory. This is done by comparing the two theories area by area. Although the predictions of quantum electrodynamics are in excellent agreement with experiment (as in the anomalous magnetic moment of the electron), there are some problems, such as the difficulty in describing the electromagnetic field with the four-component vector potential because the photon has only two polarization states. In most areas the two theories give similar results, so it is impossible to rule out the composite photon theory. Pryce's arguments in 1938 against a composite photon theory are shown to be invalid or irrelevant. Recently, it has been realized that in the composite theory the antiphoton does not interact with matter because it is formed of a neutrino and an antineutrino with the wrong helicity. This leads to experimental tests that can determine which theory is correct.

  3. Sandia Energy - Theory & Modeling

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Theory & Modeling Home Transportation Energy Predictive Simulation of Engines Combustion Chemistry Theory & Modeling Theory & ModelingAshley Otero2015-10-28T02:44:07+00:00 The CRF...

  4. Approximate Information Theory

    E-Print Network [OSTI]

    Penny, Will

    Approximate Inference Will Penny Information Theory Information Entropy Kullback-Liebler Divergence Approximate Inference Will Penny 31st March 2011 #12;Approximate Inference Will Penny Information Theory Will Penny Information Theory Information Entropy Kullback-Liebler Divergence Gaussians Asymmetry

  5. LATTICE GAUGE THEORY 1 Lattice Gauge Theory

    E-Print Network [OSTI]

    Creutz, Michael

    a crucial tool for the quantum field the- orist. Applied to the formalism of lattice gauge theory, numerical simulations are providing fundamental quantitative information about the interactions of quarksLATTICE GAUGE THEORY 1 Lattice Gauge Theory Michael Creutz Supercomputers have recently become

  6. Beyond Gauge Theories

    E-Print Network [OSTI]

    John H. Schwarz

    1998-09-01

    Superstring theory, and a recent extension called M theory, are leading candidates for a quantum theory that unifies gravity with the other forces. As such, they are certainly not ordinary quantum field theories. However, recent duality conjectures suggest that a more complete definition of these theories can be provided by the large N limits of suitably chosen U(N) gauge theories associated to the asymptotic boundary of spacetime.

  7. Quantum Optimal Control Theory

    E-Print Network [OSTI]

    J. Werschnik; E. K. U. Gross

    2007-07-12

    The control of quantum dynamics via specially tailored laser pulses is a long-standing goal in physics and chemistry. Partly, this dream has come true, as sophisticated pulse shaping experiments allow to coherently control product ratios of chemical reactions. The theoretical design of the laser pulse to transfer an initial state to a given final state can be achieved with the help of quantum optimal control theory (QOCT). This tutorial provides an introduction to QOCT. It shows how the control equations defining such an optimal pulse follow from the variation of a properly defined functional. We explain the most successful schemes to solve these control equations and show how to incorporate additional constraints in the pulse design. The algorithms are then applied to simple quantum systems and the obtained pulses are analyzed. Besides the traditional final-time control methods, the tutorial also presents an algorithm and an example to handle time-dependent control targets.

  8. Quantum Optimal Control Theory

    E-Print Network [OSTI]

    G. H. Gadiyar

    1994-05-10

    The possibility of control of phenomena at microscopic level compatible with quantum mechanics and quantum field theory is outlined. The theory could be used in nanotechnology.

  9. [Everett, 1995] J. Everett. A theory of mapping from structure to function applied to engineering thermodynamics. InProceedings of International Joint Conference on Artificial Intelligence(Montreal), pp. 1837-1843. San Mateo, CA: Morgan Kaufmann, 1995.

    E-Print Network [OSTI]

    Forbus, Kenneth D.

    components. 1 Introduction Thermodynamic cycles (e.g., power plants, refrigerators) form an important class. Virtually all electrical power generated today relies on a thermodynamic cycle in which massive boilers gene, and plant operators need to generate and test h y- potheses concerning system functions from schematics

  10. The paleoclassical interpretation of quantum theory

    E-Print Network [OSTI]

    I. Schmelzer

    2015-06-30

    This interpretation establishes a completely classical ontology -- only the classical trajectory in configuration space -- and interprets the wave function as describing incomplete information (in form of a probability flow) about this trajectory. This combines basic ideas of de Broglie-Bohm theory and Nelsonian stochastics about the trajectory with a Bayesian interpretation of the wave function. Various objections are considered and discussed. In particular a regularity principle for the zeros of the wave function allows to meet the Wallstrom objection.

  11. Theory of rheology in confinement

    E-Print Network [OSTI]

    Artem A. Aerov; Matthias Krüger

    2014-12-12

    The viscosity of fluids is generally understood in terms of kinetic mechanisms, i.e., particle collisions, or thermodynamic ones as imposed through structural distortions upon e.g. applying shear. Often the former is less relevant, and (damped) Brownian particles are considered good fluid model systems. We formulate a general theoretical approach for rheology in confinement, based on the many particle diffusion equation, evaluated via classical density functional theory. We discuss the viscosity for the situation of two parallel walls in relative motion as a function of wall-to-wall distance.

  12. Alternative analysis to perturbation theory

    E-Print Network [OSTI]

    J. Martinez-Carranza; F. Soto-Eguibar; H. Moya-Cessa

    2011-10-04

    We develop an alternative approach to time independent perturbation theory in non-relativistic quantum mechanics. The method developed has the advantage to provide in one operation the correction to the energy and to the wave function, additionally we can analyze the time evolution of the system. To verify our results, we apply our method to the harmonic oscillator perturbed by a quadratic potential. An alternative form of the Dyson series, in matrix form instead of integral form, is also obtained.

  13. ABJM theory as a Fermi gas

    E-Print Network [OSTI]

    Marcos Marino; Pavel Putrov

    2012-03-14

    The partition function on the three-sphere of many supersymmetric Chern-Simons-matter theories reduces, by localization, to a matrix model. We develop a new method to study these models in the M-theory limit, but at all orders in the 1/N expansion. The method is based on reformulating the matrix model as the partition function of an ideal Fermi gas with a non-trivial, one-particle quantum Hamiltonian. This new approach leads to a completely elementary derivation of the N^{3/2} behavior for ABJM theory and N=3 quiver Chern-Simons-matter theories. In addition, the full series of 1/N corrections to the original matrix integral can be simply determined by a next-to-leading calculation in the WKB or semiclassical expansion of the quantum gas, and we show that, for several quiver Chern-Simons-matter theories, it is given by an Airy function. This generalizes a recent result of Fuji, Hirano and Moriyama for ABJM theory. It turns out that the semiclassical expansion of the Fermi gas corresponds to a strong coupling expansion in type IIA theory, and it is dual to the genus expansion. This allows us to calculate explicitly non-perturbative effects due to D2-brane instantons in the AdS background.

  14. Functional Ecological Gene Networks to Reveal the Changes Among...

    Office of Scientific and Technical Information (OSTI)

    network structure among different microbial speciespopulations. Here, a novel random matrix theory (RMT)-based conceptual framework for identifying functional ecological gene...

  15. A Wave-function for Stringy Universes

    E-Print Network [OSTI]

    Costas Kounnas; Nicolaos Toumbas; Jan Troost

    2007-07-27

    We define a wave-function for string theory cosmological backgrounds. We give a prescription for computing its norm following an earlier analysis within general relativity. Under Euclidean continuation, the cosmologies we discuss in this paper are described in terms of compact parafermionic worldsheet systems. To define the wave-function we provide a T-fold description of the parafermionic conformal field theory, and of the corresponding string cosmology. In specific examples, we compute the norm of the wave-function and comment on its behavior as a function of moduli.

  16. Resurgent functions and splitting problems

    E-Print Network [OSTI]

    Sauzin, David

    2006-01-01

    The present text is an introduction to \\'Ecalle's theory of resurgent functions and alien calculus, in connection with problems of exponentially small separatrix splitting. An outline of the resurgent treatment of Abel's equation for resonant dynamics in one complex variable is included. The emphasis is on examples of nonlinear difference equations, as a simple and natural way of introducing the concepts.

  17. Introduction to Information Theory

    E-Print Network [OSTI]

    Belohlavek, Radim

    Introduction to Information Theory and Its Applications Radim Belohl´avek Dept. Computer Science providing introduction to Information Theory. Radim Belohl´avek, Introduction to Information Theory and Its Applications 1 #12;Information Theory: What and Why · information: one of key terms in our society

  18. A Theory of Governance

    E-Print Network [OSTI]

    Bevir, Mark

    2013-01-01

    direct interference. Proponents of governability theory stress the resources the state has at its disposal

  19. Bivariate lognormal density function 

    E-Print Network [OSTI]

    Schreyer, Glenn William

    1972-01-01

    . H. Matis and. Dr. C. K. Chui. TABLE OF CONTENTS CHAPTER Page I INTRODUCTION 1. 1 Current Status of' the Theory 1. 2 Aims of' the investigation 1. 3 Possible Applications 1 3 3 II THE PARA|%TER ESTIMATION 2. 1 Problem Description 2. 2... The Estimates RELATED PROBLHMS 3. 1 Missing Data Problem 5 1. 4 1. 6 16 3, 1. 1 Method. of Mm~ imum Likelihood 3. 1, 2 Smith-Hocking Procedure 17 19 IV 3. 2 The Hs. zard. Function MONTE CARLO STUDY 4. 1 The Simulation Problem 4. 2 The Simulation...

  20. Refined error estimates for matrix-valued radial basis functions 

    E-Print Network [OSTI]

    Fuselier, Edward J., Jr.

    2007-09-17

    Radial basis functions (RBFs) are probably best known for their applications to scattered data problems. Until the 1990s, RBF theory only involved functions that were scalar-valued. Matrix-valued RBFs were subsequently ...

  1. Exploring the limit of accuracy for density functionals based on the generalized gradient approximation: Local, global hybrid, and range-separated hybrid functionals with and without dispersion corrections

    SciTech Connect (OSTI)

    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 491 508 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 491 508 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.

  2. AdS Field Theory from Conformal Field Theory

    E-Print Network [OSTI]

    A. Liam Fitzpatrick; Jared Kaplan

    2012-08-01

    We provide necessary and sufficient conditions for a Conformal Field Theory to have a description in terms of a perturbative Effective Field Theory in AdS. The first two conditions are well-known: the existence of a perturbative `1/N' expansion and an approximate Fock space of states generated by a finite number of low-dimension operators. We add a third condition, that the Mellin amplitudes of the CFT correlators must be well-approximated by functions that are bounded by a polynomial at infinity in Mellin space, or in other words, that the Mellin amplitudes have an effective theory-type expansion. We explain the relationship between our conditions and unitarity, and provide an analogy with scattering amplitudes that becomes exact in the flat space limit of AdS. The analysis also yields a simple connection between conformal blocks and AdS diagrams, providing a new calculational tool very much in the spirit of the S-Matrix program. We also begin to explore the potential pathologies associated with higher spin fields in AdS by generalizing Weinberg's soft theorems to AdS/CFT. The AdS analog of Weinberg's argument constrains the interactions of conserved currents in CFTs, but there are potential loopholes that are unavailable to theories of massless higher spin particles in flat spacetime.

  3. Splines and Linear Control Theory Zhimin Zhang, John Tomlinson and Clyde Martin

    E-Print Network [OSTI]

    Zhang, Zhimin

    Splines and Linear Control Theory Zhimin Zhang, John Tomlinson and Clyde Martin Department and the linear control theory has been analyzed. We show that spline functions can be constructed naturally from the control theory. By establishing a framework based on control theory, we provide a simple and systematic

  4. Mesoscopic theory of the viscoelasticity of polymers

    E-Print Network [OSTI]

    S. M. Chitanvis

    1999-01-26

    We have advanced our previous static theory of polymer entanglement involving an extended Cahn-Hilliard functional, to include time-dependent dynamics. We go beyond the Gaussian approximation, to the one-loop level, to compute the frequency dependent storage and loss moduli of the system. The three parameters in our theory are obtained by fitting to available experimental data on polystyrene melts of various chain lengths. This provides a physical representation of the parameters in terms of the chain length of the system. We discuss the importance of the various terms in our energy functional with respect to their contribution to the viscoelastic response of the polymeric system.

  5. Abstracting over Semantic Theories 

    E-Print Network [OSTI]

    Holt, Alexander G B

    The topic of this thesis is abstraction over theories of formal semantics for natural language.It is motivated by the belief that a metatheoretical perspective can contribute both to a better theoretical understanding of semantic theories...

  6. Framework theories in science

    E-Print Network [OSTI]

    Henderson, Leah

    2010-01-01

    This thesis consists of three papers on the nature of scientific theories and inference. In many cases, scientific theories can be regarded as organized into hierarchies, with higher levels sometimes called 'paradigms', ...

  7. Variational Information Theory

    E-Print Network [OSTI]

    Penny, Will

    Variational Inference Will Penny Information Theory Information Entropy Kullback-Liebler Divergence Summary References Variational Inference Will Penny Bayesian Inference Course, WTCN, UCL, March 2013 #12;Variational Inference Will Penny Information Theory Information Entropy Kullback-Liebler Divergence Gaussians

  8. Eisenstein Series in String Theory

    E-Print Network [OSTI]

    N. A. Obers; B. Pioline

    2000-03-01

    We discuss the relevance of Eisenstein series for representing certain G(Z)-invariant string theory amplitudes which receive corrections from BPS states only. The Eisenstein series are constructed using G(Z)-invariant mass formulae and are manifestly invariant modular functions on the symmetric space K\\G(R) of non-compact type, with K the maximal compact subgroup of G(R). In particular, we show how Eisenstein series of the T-duality group SO(d,d,Z) can be used to represent one- and g-loop amplitudes in compactified string theory. We also obtain their non-perturbative extensions in terms of the Eisenstein series of the U-duality group E_{d+1(d+1)}(Z).

  9. Comment on “Correlation and relativistic effects in U metal and U-Zr alloy: Validation of ab initio approaches”

    SciTech Connect (OSTI)

    Söderlind, 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.

  10. Topological quantum field theories

    E-Print Network [OSTI]

    Albert Schwarz

    2000-11-29

    Following my plenary lecture on ICMP2000 I review my results concerning two closely related topics: topological quantum field theories and the problem of quantization of gauge theories. I start with old results (first examples of topological quantum field theories were constructed in my papers in late seventies) and I come to some new results, that were not published yet.

  11. Tactics for male reproductive success in plants: contrasting insights of sex allocation theory and pollen presentation theory

    E-Print Network [OSTI]

    Thomson, James D.

    allocation theory is that an organism's reproductive success, through either male or female function, can in that function. The shapes of these curves determine what patterns of resource allocation can be evolutionarily and female pathways, to the amount of resources it invested in male and female function. Sex allocation

  12. New second derivative theories of gravity for spherically symmetric spacetimes

    E-Print Network [OSTI]

    Rakesh Tibrewala

    2015-03-17

    We present new second derivative, generally covariant theories of gravity for spherically symmetric spacetimes (general covariance is in the $t-r$ plane) belonging to the class where the spherically symmetric Einstein-Hilbert theory is modified by the presence of $g_{\\theta\\theta}$ dependent functions. In $3+1$ dimensional vacuum spacetimes there is three-fold infinity of freedom in constructing such theories as revealed by the presence of three arbitrary $g_{\\theta\\theta}$ dependent functions in the Hamiltonian (matter Hamiltonian also has the corresponding freedom). This result is not a contradiction to the theorem of Hojman et. al. [1] which is applicable to the full theory whereas the above conclusion is for symmetry reduced sector of the theory (which has a much reduced phase space). In the full theory where there are no special symmetries, the result of Hojman et. al. will continue to hold. In the process we also show that theories where the constraint algebra is deformed by the presence of $g_{\\theta\\theta}$ dependent functions - as is the case in the presence of inverse triad corrections in loop quantum gravity - can always be brought to the form where they obey the standard (undeformed) constraint algebra by performing a suitable canonical transformation. We prove that theories obtained after performing canonical transformation are inequivalent to the symmetry reduced general relativity and that the resulting theories fall within the purview of the theories mentioned above.

  13. Review: Theories of Sustainable Development

    E-Print Network [OSTI]

    Laberge, Yves

    2015-01-01

    Review: Theories of Sustainable Development Edited By JudithTheories of Sustainable Development. Abingdon: Routledge,Routledge Studies in Sustainable Development. Theories of

  14. Gauge theories on noncommutative spaces

    E-Print Network [OSTI]

    Albert Schwarz

    2000-11-29

    I review my results about noncommutative gauge theories and about the relation of these theories to M(atrix) theory following my lecture on ICMP 2000.

  15. Evolution of the coupling constant in SU(2) lattice gauge theory with two adjoint fermions

    E-Print Network [OSTI]

    Ari J. Hietanen; Kari Rummukainen; Kimmo Tuominen

    2009-11-24

    We measure the evolution of the coupling constant using the Schroedinger functional method in the lattice formulation of SU(2) gauge theory with two massless Dirac fermions in the adjoint representation. We observe strong evidence for an infrared fixed point, where the theory becomes conformal. We measure the continuum beta-function and the coupling constant as a function of the energy scale.

  16. Active Oxygen Vacancy Site for Methanol Synthesis from CO2 Hydrogenation on In2O3(110): A DFT Study

    SciTech Connect (OSTI)

    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.

  17. String Theory Symmetries

    E-Print Network [OSTI]

    John H. Schwarz

    1995-03-20

    A brief review of the status of duality symmetries in string theory is presented. The evidence is accumulating rapidly that an enormous group of duality symmetries, including perturbative T dualities and non-perturbative S-dualities, underlies string theory. It is my hope that an understanding of these symmetries will suggest the right way to formulate non-perturbative string theory. Whether or not this hope is realized, it has already been demonstrated that this line of inquiry leads to powerful new tools for understanding gauge theories and new evidence for the uniqueness of string theory, as well as deep mathematical results.

  18. Exact Results in Supersymmetric Gauge Theories

    E-Print Network [OSTI]

    Saulius Valatka

    2014-12-31

    In this thesis we discuss supersymmetric gauge theories, focusing on exact results achieved using methods of integrability. For the larger portion of the thesis we study the N=4 super Yang-Mills theory in the planar limit, a recurring topic being the Konishi anomalous dimension, which is roughly the analogue for the mass of the proton in quantum chromodynamics. The N=4 supersymmetric Yang-Mills theory is known to be integrable in the planar limit, which opens up a wealth of techniques one can employ in order to find results in this limit valid at any value of the coupling. We begin with perturbation theory where the integrability of the theory first manifests itself. Here we showcase the first exact result, the so-called slope function, which is the linear small spin expansion coefficient of the generalized Konishi anomalous dimension. We then move on to exact results mainly achieved using the novel quantum spectral curve approach, the method allowing one to find scaling dimensions of operators at arbitrary values of the coupling. As an example we find the second coefficient in the small spin expansion after the slope, which we call the curvature function. This allows us to extract non-trivial information about the Konishi operator. Methods of integrability are also applicable to other supersymmetric gauge theories such as ABJM, which in fact shares many similarities with N=4 super Yang-Mills. We briefly review these parallel developments in the last chapter of the thesis.

  19. Matrix theory of gravitation

    E-Print Network [OSTI]

    Wolfgang Koehler

    2011-03-23

    A new classical theory of gravitation within the framework of general relativity is presented. It is based on a matrix formulation of four-dimensional Riemann-spaces and uses no artificial fields or adjustable parameters. The geometrical stress-energy tensor is derived from a matrix-trace Lagrangian, which is not equivalent to the curvature scalar R. To enable a direct comparison with the Einstein-theory a tetrad formalism is utilized, which shows similarities to teleparallel gravitation theories, but uses complex tetrads. Matrix theory might solve a 27-year-old, fundamental problem of those theories (sec. 4.1). For the standard test cases (PPN scheme, Schwarzschild-solution) no differences to the Einstein-theory are found. However, the matrix theory exhibits novel, interesting vacuum solutions.

  20. Non-Lagrangian Theories from Brane Junctions

    E-Print Network [OSTI]

    Ling Bao; Vladimir Mitev; Elli Pomoni; Masato Taki; Futoshi Yagi

    2013-11-08

    In this article we use 5-brane junctions to study the 5D T_N SCFTs corresponding to the 5D N=1 uplift of the 4D N=2 strongly coupled gauge theories, which are obtained by compactifying N M5 branes on a sphere with three full punctures. Even though these theories have no Lagrangian description, by using the 5-brane junctions proposed by Benini, Benvenuti and Tachikawa, we are able to derive their Seiberg-Witten curves and Nekrasov partition functions. We cross-check our results with the 5D superconformal index proposed by Kim, Kim and Lee. Through the AGTW correspondence, we discuss the relations between 5D superconformal indices and n-point functions of the q-deformed W_N Toda theories.

  1. The "Unromantic Pictures" of Quantum Theory

    E-Print Network [OSTI]

    Roderich Tumulka

    2006-07-18

    I am concerned with two views of quantum mechanics that John S. Bell called ``unromantic'': spontaneous wave function collapse and Bohmian mechanics. I discuss some of their merits and report about recent progress concerning extensions to quantum field theory and relativity. In the last section, I speculate about an extension of Bohmian mechanics to quantum gravity.

  2. Photoelectron Spectroscopy Claudia Rdl and Matteo Gatti

    E-Print Network [OSTI]

    Botti, Silvana

    theory (MBPT) Ground state structural properties total energies charge densities One-particle excitations-functional theory (DFT) Many-body perturbation theory (MBPT) Ground state structural properties total energies06 HSE06+G0 W0 HSE06+Gn W0 Experiment Ghijsen et al. (1988) -20 -15 -10 -5 0 5 10 15 energy [eV] PBE

  3. Communication Theory JOINT IMPULSE RESPONSE SHORTENING

    E-Print Network [OSTI]

    Adali, Tulay

    channel environments by adjusting the energy and constellation size of each carrier. One implementation of MCM is the Discrete Multi-tone (DMT) system which uses the discrete Fourier transform (DFT) for modulation [2], [3]., DMT has recently been cho- sen as the industry modulation standard for Asymmetri- cal

  4. MULTIVARIATE OUTLYINGNESS FUNCTIONS MAHALANOBIS TYPE OUTLYINGNESS FUNCTIONS

    E-Print Network [OSTI]

    Serfling, Robert

    OUTLINE MULTIVARIATE OUTLYINGNESS FUNCTIONS MAHALANOBIS TYPE OUTLYINGNESS FUNCTIONS ADDITION MULTIVARIATE OUTLYINGNESS FUNCTIONS MAHALANOBIS TYPE OUTLYINGNESS FUNCTIONS ADDITION AND REPLACEMENT BREAKDOWN Criterion Robert Serfling NONPARAMETRIC OUTLIER IDENTIFICATION #12;OUTLINE MULTIVARIATE OUTLYINGNESS

  5. Motivation and Outline Hatree-Fock Theory and KLI Approximation

    E-Print Network [OSTI]

    Holzwarth, Natalie

    Motivation and Outline Hatree-Fock Theory and KLI Approximation Frozen core orbital approximation March 24, 2011 Xiao Xu, N. A. W. Holzwarth PAW + HF & KLI #12;Motivation and Outline Hatree-Fock Theory of HF and KLI Conclusion Outline 1 Motivation of this work: Why? orbital dependent functionals + PAW 2

  6. Finding True Beliefs: Applying Rank-Dependent Expected Utility Theory

    E-Print Network [OSTI]

    Chen, Yiling

    -making that incorporates probability weighting and non-linear utility functions, to the analysis of the quadratic scoringFinding True Beliefs: Applying Rank-Dependent Expected Utility Theory to Proper Scoring Rules-value maximizers. Thus, we apply rank-dependent expected utility theory, a more general model of decision

  7. The Solar $hep$ Processes in Effective Field Theory

    E-Print Network [OSTI]

    Tae-Sun Park; Kuniharu Kubodera; Dong-Pil Min; Mannque Rho

    2001-10-31

    By combining effective field theory with the standard nuclear physics approach (SNPA) we obtain a high-precision estimate of the $S$ factor for the solar $hep$ process. The accurate wave functions available in SNPA are used to evaluate the nuclear matrix elements for the transition operators that result from chiral perturbation theory (ChPT). All the contributions up to \

  8. A review on SUSY gauge theories on $S^3$

    E-Print Network [OSTI]

    Kazuo Hosomichi

    2015-07-04

    This is the 9th article in the collection of reviews "Exact results on N=2 supersymmetric gauge theories", ed. J.Teschner. We review the exact computations in 3D N=2 supersymmetric gauge theories on the round or squashed $S^3$ and the relation between 3D partition functions and 4D superconformal indices.

  9. Theory and Modeling of Weakly Bound/Physisorbed Materials

    E-Print Network [OSTI]

    by physisorption: ­ CNT, fullerenes, carbon aerogels ­ Doping, Decorating, Charging · Accuracy of Methods: DFT, QMC CNT may have increased absorption3 · Carbon aerogels4 have exhibited 5 wt% for high surface areas, ~1

  10. Topological Field Theory Amplitudes for $A_{N-1}$ Fibration

    E-Print Network [OSTI]

    Iqbal, Amer; Qureshi, Babar A; Shabbir, Khurram; Shehper, Muhammad A

    2015-01-01

    We study the partition function ${\\cal N}=1$ 5D $U(N)$ gauge theory with $g$ adjoint hypermultiplets and show that for massless adjoint hypermultiplets it is equal to the partition function of a two dimensional topological field on a genus $g$ Riemann surface. We describe the topological field theory by its amplitudes associated with cap, propagator and pair of pants. These basic amplitudes are open topological string amplitudes associated with certain Calabi-Yau threefolds in the presence of Lagrangian branes.

  11. Mesoscopic theory for inhomogeneous mixtures

    E-Print Network [OSTI]

    A. Ciach

    2010-10-22

    Mesoscopic density functional theory for inhomogeneous mixtures of sperical particles is developed in terms of mesoscopic volume fractions by a systematic coarse-graining procedure starting form microscopic theory. Approximate expressions for the correlation functions and for the grand potential are obtained for weak ordering on mesoscopic length scales. Stability analysis of the disordered phase is performed in mean-field approximation (MF) and beyond. MF shows existence of either a spinodal or a $\\lambda$-surface on the volume-fractions - temperature phase diagram. Separation into homogeneous phases or formation of inhomogeneous distribution of particles occurs on the low-temperature side of the former or the latter surface respectively, depending on both the interaction potentials and the size ratios between particles of different species. Beyond MF the spinodal surface is shifted, and the instability at the $\\lambda$-surface is suppressed by fluctuations. We interpret the $\\lambda$-surface as a borderline between homogeneous and inhomogeneous (containing clusters or other aggregates) structure of the disordered phase. For two-component systems explicit expressions for the MF spinodal and $\\lambda$-surfaces are derived. Examples of interaction potentials of simple form are analyzed in some detail, in order to identify conditions leading to inhomogeneous structures.

  12. On KP-integrable Hurwitz functions

    E-Print Network [OSTI]

    Alexandrov, A; Morozov, A; Natanzon, S

    2014-01-01

    There is now a renewed interest to the Hurwitz tau-function, counting the isomorphism classes of Belyi pairs, arising in the study of equilateral triangulations and Grothiendicks's dessins d'enfant. It is distinguished by belonging to a particular family of Hurwitz tau-functions, possessing conventional Toda/KP integrability properties. We explain how the variety of recent observations about this function fits into the general theory of matrix model tau-functions. All such quantities possess a number of different descriptions, related in a standard way: these include Toda/KP integrability, several kinds of W-representations (we describe four), two kinds of integral (multi-matrix model) descriptions (of Hermitian and Kontsevich types), Virasoro constraints, character expansion, embedding into generic set of Hurwitz tau-functions and relation to knot theory. When approached in this way, the family of models in the literature has a natural extension, and additional integrability with respect to associated new ti...

  13. Theory Modeling and Simulation

    SciTech Connect (OSTI)

    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.

  14. Automated Lattice Perturbation Theory

    SciTech Connect (OSTI)

    Monahan, Christopher

    2014-11-01

    I review recent developments in automated lattice perturbation theory. Starting with an overview of lattice perturbation theory, I focus on the three automation packages currently "on the market": HiPPy/HPsrc, Pastor and PhySyCAl. I highlight some recent applications of these methods, particularly in B physics. In the final section I briefly discuss the related, but distinct, approach of numerical stochastic perturbation theory.

  15. Number Theory Seminar

    E-Print Network [OSTI]

    $author.value

    2014-12-03

    Dec 3, 2014 ... TBA, Rachel Davis ... September 26, Rachel Davis .... Dessins d'Enfants · Indiana Pi Bill · Notes and Publications · Number Theory Seminar ...

  16. Effective medium theory

    SciTech Connect (OSTI)

    Krokhin, Arkadii [Univ. of North Texas, Denton, TX (United States)

    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.

  17. Theory of Relaxor Ferroelectrics

    E-Print Network [OSTI]

    Guzman-Verri, Gian Giacomo

    2012-01-01

    Theory of Thermal Neutron Scattering: the Use of Neutronsdetermined from neutron scattering. [39] A symmetry analysis9, 10] Only recently neutron scattering experiments have

  18. Smith Theory Revisited

    E-Print Network [OSTI]

    1997-10-15

    Smith Theory Revisited. William G. Dwyer. Clarence W. Wilkerson. ?. 1 Introduction. In the late 1930's, P. A. Smith began the investigation of the cohomological.

  19. Spectral Graph Theory

    E-Print Network [OSTI]

    *D. J. Kelleher

    2011-09-30

    Spectral Graph Theory. *D. J. Kelleher2. 2Department of Mathematics. University of Connecticut. UConn— SIGMA Seminar — Fall 2011. D. J. Kelleher. Spectral ...

  20. A Theory of Governance

    E-Print Network [OSTI]

    Bevir, Mark

    2013-01-01

    Trentmann, “The Modern Genealogy of the Consumer: Meanings,2007. Biebricher, T. “Genealogy and Governmentality. ”of Political Theory: The Genealogy of an American Vocation.