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Relativistic Effects From Coupled-Cluster Theory

Other · · Comprehensive Computational Chemistry
 [1]
  1. Johns Hopkins University, Baltimore, MD (United States); Johns Hopkins University
+ Show Author Affiliations
In this chapter we first discuss the theory and computational challenges of the relativistic coupled-cluster methods. Example calculations of heavy-atom-containing molecules are then presented to demonstrate the importance of scalar-relativistic, spin-orbit coupling, and electron-correlation effects on molecular properties as well as the applicability and usefulness of relativistic coupled-cluster methods in calculations aiming at high-accuracy results. A unique applicability of the spinor-based relativistic coupled-cluster methods is also highlighted using the calculations of open shell actinide-containing small molecules. As a result, a summary is given together with an outlook into future developments.
Research Organization:
Johns Hopkins University, Baltimore, MD (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
DOE Contract Number:
SC0020317
OSTI ID:
2349510
Country of Publication:
United States
Language:
English

References (188)

Simple recipe for implementing computation of first-order relativistic corrections to electron correlation energies in framework of direct perturbation theory journal January 1997
Investigation of an asymmetric triple-excitation correction for coupled-cluster energies journal January 1998
Spin–orbit coupling and electron correlation in relativistic configuration interaction and coupled-cluster methods journal February 2012
High accuracy theoretical investigations of CaF, SrF, and BaF and implications for laser-cooling journal July 2019
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
Non-orthogonal spin-adaptation of coupled cluster methods: A new implementation of methods including quadruple excitations journal February 2015
Symmetry exploitation in closed-shell coupled-cluster theory with spin-orbit coupling journal July 2011
On the spin separation of algebraic two-component relativistic Hamiltonians: Molecular properties journal August 2014
Relativistic coupled‐cluster and equation‐of‐motion coupled‐cluster methods journal May 2021
The Thermodynamic Properties of the f -Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides journal March 2014
Douglas–Kroll–Hess Theory: a relativistic electrons-only theory for chemistry journal January 2006
Taming the low-lying electronic states of FeH journal December 2012
Implementation of Relativistic Coupled Cluster Theory for Massively Parallel GPU-Accelerated Computing Architectures journal August 2021
Communication: Theoretical study of HfF + cation to search for the T,P-odd interactions journal July 2017
Determining nuclear quadrupole moments of Bi and Sb from molecular data journal January 2023
Application of relativistic coupled-cluster theory to the effective electric field in YbF journal August 2014
The relativistic Fock-space coupled-cluster method for molecules: CdH and its ions journal March 1998
Tensor Contraction Engine:  Abstraction and Automated Parallel Implementation of Configuration-Interaction, Coupled-Cluster, and Many-Body Perturbation Theories journal November 2003
Mercury Monohalides: Suitability for Electron Electric Dipole Moment Searches journal May 2015
The route to high accuracy in ab initio calculations of Cu quadrupole-coupling constants journal December 2012
On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell‐Type Expansion Using Quantum‐Field Theoretical Methods journal December 1966
Inclusion of mean-field spin–orbit effects based on all-electron two-component spinors: Pilot calculations on atomic and molecular properties journal December 2001
Relativistic and correlation effects on molecular properties. II. The hydrogen halides HF, HCl, HBr, HI, and HAt journal August 1996
Theoretical Chemistry of Gold journal August 2004
Similarity-transformed equation-of-motion coupled-cluster singles and doubles method with spin-orbit effects for excited states journal October 2019
Enhancement factor for the electric dipole moment of the electron in the BaOH and YbOH molecules journal April 2019
The Hyperfine Structures of CuCl and CuBr in Their Ground States Studied by Microwave Fourier Transform Spectroscopy journal October 1993
High Accuracy Quantum Chemical and Thermochemical Network Data for the Heats of Formation of Fluorinated and Chlorinated Methanes and Ethanes journal June 2018
The Chronus Quantum software package journal August 2019
Analytic energy gradients in closed-shell coupled-cluster theory with spin-orbit coupling journal November 2008
Spin-orbit effects calculated by two-component coupled-cluster methods: test calculations on AuH, Au2, TlH and Tl2 journal August 1998
Formation, microwave spectrum and molecular constants of bismuth monochloride journal December 1976
Multireference configuration interaction calculations of the first six ionization potentials of the uranium atom journal November 2015
Two-Component Relativistic Equation-of-Motion Coupled-Cluster Methods for Excitation Energies and Ionization Potentials of Atoms and Molecules journal October 2016
The rotational spectrum of CuCCH(X̃ Σ1+): A Fourier transform microwave discharge assisted laser ablation spectroscopy and millimeter/submillimeter study journal November 2010
Relativistic perturbation theory. I. A new perturbation approach to the Dirac equation journal January 1986
Generalized relativistic effective core potential and relativistic coupled cluster calculation of the spectroscopic constants for the HgH molecule and its cation journal August 2001
Foundations of the relativistic theory of many-electron atoms journal August 1980
Relativistic Hartree–Fock by means of stationary direct perturbation theory. I. General theory journal January 1995
An atomic mean-field spin-orbit approach within exact two-component theory for a non-perturbative treatment of spin-orbit coupling journal April 2018
Coupled-cluster method for open-shell heavy-element systems with spin-orbit coupling journal April 2017
Conclusive determination of ethynyl radical hydrogen abstraction energetics and kinetics* journal June 2020
The relativistic four-component coupled cluster method for molecules: spectroscopic constants of SnH4 journal January 1996
Relativistic coupled-cluster static dipole polarizabilities of the alkali metals from Li to element 119 journal October 1999
Complete characterization of the 3p Rydberg complex of a molecular ion: MgAr + . I. Observation of the Mg(3pσ)Ar + B + state and determination of its structure and dynamics journal August 2020
Approximate treatment of higher excitations in coupled-cluster theory journal December 2005
Short-range correlations in nuclear wave functions journal June 1960
The accuracy of the pseudopotential approximation. II. A comparison of various core sizes for indium pseudopotentials in calculations for spectroscopic constants of InH, InF, and InCl journal July 1996
Two-component calculations for the molecules containing superheavy elements: Spin–orbit effects for (117)H, (113)H, and (113)F journal May 1999
General implementation of the relativistic coupled-cluster method journal December 2010
Atomic Mean-Field Approach within Exact Two-Component Theory Based on the Dirac–Coulomb–Breit Hamiltonian journal June 2022
Application of the finite-field coupled-cluster method to calculate molecular properties relevant to electron electric-dipole-moment searches journal March 2018
Two-component spin–orbit calculations for the hetero diatomic molecules TlAt and (113)(117) with relativistic effective core potentials journal June 2003
A relativistic coupled-cluster interaction potential and rovibrational constants for the xenon dimer journal August 2017
Nuclear electric quadrupole moment of bismuth from the molecular method journal November 2013
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients journal June 1993
Invited review: Relativistic wave-function based electron correlation methods journal February 2012
W4 theory for computational thermochemistry: In pursuit of confident sub-kJ/mol predictions journal October 2006
Nuclear electric quadrupole moment of gold journal February 2007
Theoretical Analysis of the Bonding between CO and Positively Charged Atoms journal December 1997
A fifth-order perturbation comparison of electron correlation theories journal May 1989
The generalized Douglas–Kroll transformation journal November 2002
Coupled-cluster approach to molecular structure and spectra: a step toward predictive quantum chemistry journal March 1989
Year-2017 nuclear quadrupole moments journal February 2018
Perturbative treatment of spin-orbit-coupling within spin-free exact two-component theory using equation-of-motion coupled-cluster methods journal January 2018
A coupled cluster approach with triple excitations journal December 1984
Infinite-order two-component theory for relativistic quantum chemistry journal February 2002
Relativistic all-electron coupled-cluster calculations on Au2 in the framework of the Douglas–Kroll transformation journal January 2000
Towards a full CCSDT model for electron correlation. CCSDT-n models journal February 1987
Spin-orbit coupling constants from coupled-cluster response theory journal January 2000
Relativistic coupled-cluster calculation of the electron-nucleus scalar-pseudoscalar interaction constant W s in YbF journal April 2016
Equation-of-motion coupled-cluster theory based on the 4-component Dirac–Coulomb(–Gaunt) Hamiltonian. Energies for single electron detachment, attachment, and electronically excited states journal November 2018
Spin–orbit coupling and electron correlation at various coupled-cluster levels for closed-shell diatomic molecules journal January 2013
Formulation and implementation of the relativistic Fock-space coupled cluster method for molecules journal December 2001
Exact two-component Hamiltonians revisited journal July 2009
Analytic evaluation of first-order properties within the mean-field variant of spin-free exact two-component theory journal May 2019
Relativistic corrections to electrical first-order properties using direct perturbation theory journal October 2008
Electric dipole moments generated by nuclear Schiff moment interactions: A reassessment of the atoms Xe129 and Hg199 and the molecule TlF205 journal August 2022
In search of the electron dipole moment:Ab initiocalculations onPbO207excited states journal March 2004
Analytical evaluation of first-order electrical properties based on the spin-free Dirac-Coulomb Hamiltonian journal June 2011
A comparison between hydrogen and halogen bonding: the hypohalous acid–water dimers, HOX⋯H 2 O (X = F, Cl, Br) journal January 2019
Route to Chemical Accuracy for Computational Uranium Thermochemistry journal October 2022
An arbitrary order Douglas–Kroll method with polynomial cost journal January 2009
Why CCSD(T) works: a different perspective journal December 1997
Enhanced P,T-violating nuclear magnetic quadrupole moment effects in laser-coolable molecules journal February 2020
Towards accurate prediction for laser-coolable molecules: relativistic coupled-cluster calculations for yttrium monoxide and prospects for improving its laser cooling efficiencies journal January 2020
Analytic Self-Consistent Field Wavefunctions and Computed Properties for Homonuclear Diatomic Molecules journal November 1964
Relativistic regular two‐component Hamiltonians journal September 1993
Coupled-cluster methods including noniterative corrections for quadruple excitations journal August 2005
Further benchmarks of a composite, convergent, statistically calibrated coupled-cluster-based approach for thermochemical and spectroscopic studies journal April 2012
Prediction of Bond Dissociation Energies/Heats of Formation for Diatomic Transition Metal Compounds: CCSD(T) Works journal January 2017
Fully relativistic coupled cluster and DFT study of electric field gradients at Hg in 199Hg compounds journal January 2012
Accurate Ionization Potentials for UO and UO 2 :  A Rigorous Test of Relativistic Quantum Chemistry Calculations journal June 2003
Application of the Correlation Consistent Composite Approach (ccCA) to Third-Row (Ga−Kr) Molecules journal January 2008
The nuclear electric quadrupole moment of antimony from the molecular method journal August 2006
Analytic evaluation of energy first derivatives for spin–orbit coupled-cluster singles and doubles augmented with noniterative triples method: General formulation and an implementation for first-order properties journal February 2021
Modeling the OH-Initiated Oxidation of Mercury in the Global Atmosphere without Violating Physical Laws journal December 2019
Coupled‐cluster method truncated at quadruples journal November 1991
Perturbative treatment of scalar-relativistic effects in coupled-cluster calculations of equilibrium geometries and harmonic vibrational frequencies using analytic second-derivative techniques journal July 2007
Millimeter wave spectrum of gaseous bismuth monofluoride (BiF) journal August 1977
Two-component relativistic coupled-cluster methods using mean-field spin-orbit integrals journal January 2018
Exact decoupling of the Dirac Hamiltonian. II. The generalized Douglas–Kroll–Hess transformation up to arbitrary order journal January 2004
Spin–orbit effects for the diatomic molecules containing halogen elements studied with relativistic effective core potentials: HX, X2 (X=Cl, Br and I) and IZ (Z=F, Cl and Br) molecules journal April 2005
Accurate and efficient treatment of two-electron contributions in quasirelativistic high-order Douglas-Kroll density-functional calculations journal November 2005
Relativistic Fock space coupled-cluster study of bismuth electronic structure to extract the Bi nuclear quadrupole moment journal September 2021
Kramers-restricted closed-shellCCSD theory journal February 1995
A mean-field spin-orbit method applicable to correlated wavefunctions journal March 1996
Analytic energy gradients for the spin-free exact two-component theory using an exact block diagonalization for the one-electron Dirac Hamiltonian journal August 2011
Recursive intermediate factorization and complete computational linearization of the coupled-cluster single, double, triple, and quadruple excitation equations journal January 1991
Spin-orbit-resolved static polarizabilities of group-13 atoms: Four-component relativistic configuration interaction and coupled cluster calculations journal November 2005
A Computational Assessment of Actinide Dioxide Cations AnO 2 2+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O═An═O] 2+ journal March 2020
Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations journal August 2015
Bond Dissociation Energies for Diatomic Molecules Containing 3d Transition Metals: Benchmark Scalar-Relativistic Coupled-Cluster Calculations for 20 Molecules journal February 2017
Relativity and the periodic system of elements journal August 1979
On the Spectroscopic and Thermochemical Properties of ClO, BrO, IO, and Their Anions journal December 2006
Relativistic general-order coupled-cluster method for high-precision calculations: Application to the Al + atomic clock journal March 2011
The higher-order Douglas–Kroll transformation journal November 2000
Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium journal September 2019
The DIRAC code for relativistic molecular calculations journal May 2020
Quasirelativistic theory equivalent to fully relativistic theory journal December 2005
RIMS measurements for the determination of the first ionization potential of the actinides actinium up to einsteinium
  • Waldek, Achim
  • RESONANCE IONIZATION SPECTROSCOPY 2000: Laser Ionization and Applications Incorporating RIS; 10th International Symposium, AIP Conference Proceedings https://doi.org/10.1063/1.1405607
conference January 2001
Calculation of response properties with the normalized elimination of the small component method journal November 2013
A direct product decomposition approach for symmetry exploitation in many‐body methods. I. Energy calculations journal March 1991
An Introduction to Coupled Cluster Theory for Computational Chemists book January 2000
The CC3 model: An iterative coupled cluster approach including connected triples journal February 1997
Closed-shell interaction in silver and gold chlorides journal August 1998
Structure and Bonding of the Transition-Metal Carbonyl Complexes M(CO) 5 L (M = Cr, Mo, W) and M(CO) 3 L (M = Ni, Pd, Pt; L = CO, SiO, CS, N 2 , NO + , CN - , NC - , HCCH, CCH 2 , CH 2 , CF 2 , H 2 ) 1 journal January 1996
Development and application of the analytical energy gradient for the normalized elimination of the small component method journal June 2011
The full CCSDT model for molecular electronic structure journal June 1987
The initial implementation and applications of a general active space coupled cluster method journal November 2000
Open-shell relativistic coupled-cluster method with Dirac-Fock-Breit wave functions: Energies of the gold atom and its cation journal March 1994
Interfacing relativistic and nonrelativistic methods. I. Normalized elimination of the small component in the modified Dirac equation journal June 1997
Relativistic Real-Time Time-Dependent Equation-of-Motion Coupled-Cluster journal October 2019
Ab initio calculations of the ground-state electron affinities of gallium and indium journal December 1999
Formulation and implementation of a relativistic unrestricted coupled‐cluster method including noniterative connected triples journal November 1996
Electronic Structure and Bonding Situation in M 2 O 2 (M = Be, Mg, Ca) Rhombic Clusters journal February 2018
Stability conditions and nuclear rotations in the Hartree-Fock theory journal November 1960
General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions journal July 2019
Exact two-component equation-of-motion coupled-cluster singles and doubles method using atomic mean-field spin-orbit integrals journal February 2019
Relativistic effects at the correlated level. An application to interhalogens journal December 1993
Toward Accurate Theoretical Thermochemistry of First Row Transition Metal Complexes journal December 2011
Measuring the electric dipole moment of the electron in BaF journal November 2018
The MRCC program system: Accurate quantum chemistry from water to proteins journal February 2020
Systematic study and uncertainty evaluation of P , T -odd molecular enhancement factors in BaF journal July 2021
Laser-coolable AcOH+ ion for CP -violation searches journal February 2022
Large-scale electron correlation calculations in the framework of the spin-free dirac formalism: the Au2 molecule revisited journal April 2005
An exact separation of the spin‐free and spin‐dependent terms of the Dirac–Coulomb–Breit Hamiltonian journal February 1994
Bound states of a many-particle system journal June 1958
On the construction of double group molecular symmetry functions journal April 1996
Equation-of-motion coupled-cluster methods for atoms and molecules in strong magnetic fields journal April 2017
Coupled-cluster theory in quantum chemistry journal February 2007
Correlation problems in atomic and molecular systems III. Rederivation of the coupled-pair many-electron theory using the traditional quantum chemical methodst journal July 1971
Molecular structure determination: Equilibrium structure of pyrimidine ( m -C 4 H 4 N 2 ) from rotational spectroscopy ( r e SE ) and high-level ab initio calculation ( r e ) agree within the uncertainty of experimental measurement journal March 2020
A relativistic 4-component general-order multi-reference coupled cluster method: initial implementation and application to HBr journal March 2007
Exact two-component Hamiltonians for relativistic quantum chemistry: Two-electron picture-change corrections made simple journal September 2022
Noble gas–metal chemical bonding? The microwave spectra, structures, and hyperfine constants of Ar–CuX(X=F, Cl, Br) journal June 2000
Four-Component Relativistic Coupled Cluster and Configuration Interaction Calculations on the Ground and Excited States of the RbYb Molecule † journal November 2009
Quantitative Computational Thermochemistry of Transition Metal Species † journal November 2007
A new implementation of the full CCSDT model for molecular electronic structure journal November 1988
Electronic spectroscopy and ionization potential of UO2 in the gas phase journal March 2004
Microwave spectra, nuclear field shift effects, geometries and hyperfine constants of bismuth mononitride, BiN, and bismuth monophosphide, BiP journal June 2004
Evaluation of CP violation in HfF + journal October 2018
Two-component methods of relativistic quantum chemistry: from the Douglas–Kroll approximation to the exact two-component formalism journal October 2001
Relativistic effects in structural chemistry journal May 1988
Relativistic all-electron coupled-cluster calculations on the gold atom and gold hydride in the framework of the douglas-kroll transformation journal November 1994
Higher excitations in coupled-cluster theory journal August 2001
Relativistic Coupled Cluster Calculations with Variational Quantum Electrodynamics Resolve the Discrepancy between Experiment and Theory Concerning the Electron Affinity and Ionization Potential of Gold journal January 2017
Interfacing relativistic and nonrelativistic methods. IV. One- and two-electron scalar approximations journal November 2001
Geometry optimizations with spinor-based relativistic coupled-cluster theory journal April 2022
Hyperfine structure in the Ω=0+ ground state of bismuth iodide (Bil) journal November 1981
The coupled‐cluster single, double, triple, and quadruple excitation method journal September 1992
Effect of the neutron quadrupole distribution in the TaO+ cation journal April 2022
Relatives of cyanomethylene: replacement of the divalent carbon by B − , N + , Al − , Si, P + , Ga − , Ge, and As + journal January 2019
A point-charge model for the nuclear quadrupole moment: Coupled-cluster, Dirac–Fock, Douglas–Kroll, and nonrelativistic Hartree–Fock calculations for the Cu and F electric field gradients in CuF journal April 1998
Perspective: Relativistic effects journal April 2012
Relativistic electronic-structure calculations employing a two-component no-pair formalism with external-field projection operators journal June 1986
Molecular density functional calculations in the regular relativistic approximation: Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and comparison with first-order relativistic calculations journal July 1998
Communication: Spin-orbit splittings in degenerate open-shell states via Mukherjee's multireference coupled-cluster theory: A measure for the coupling contribution journal March 2012
A Lagrangian framework for deriving triples and quadruples corrections to the CCSD energy journal February 2014
P , T -odd and magnetic hyperfine-interaction constants and excited-state lifetime for HfF + journal October 2017
Relativistic and correlation effects on molecular properties. I. The dihalogens F 2 , Cl 2 , Br 2 , I 2 , and At 2 journal June 1996
Analytic one-electron properties at the 4-component relativistic coupled cluster level with inclusion of spin-orbit coupling journal November 2016
Analytic second derivatives in closed-shell coupled-cluster theory with spin-orbit coupling journal October 2009
Analytic energy derivatives in relativistic quantum chemistry journal February 2014
Perturbative calculation of spin-orbit splittings using the equation-of-motion ionization-potential coupled-cluster ansatz journal November 2008
Fifth‐order many‐body perturbation theory for molecular correlation energies journal June 1989
Predictive Simulations of Ionization Energies of Solvated Halide Ions with Relativistic Embedded Equation of Motion Coupled Cluster Theory journal December 2018
Relativistic effects on chemical properties journal August 1979

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Relativistic effects
actinide chemistry
coupled cluster theory