Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling

Abstract

The paper reports development of an atomic mean-field (AMF) spin–orbit approach within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e), a new relativistic quantum-chemical method for treating spin-orbit coupling in molecules. The effective one-electron spin–orbit integral matrix in the four-component representation is assembled as a direct sum of one-centre spin–orbit integral matrices with the mean-field two-electron contributions evaluated using atomic SFX2C-1e Hartree–Fock density matrices. It is then transformed into two-component representation using analytic SFX2C-1e energy derivative formulation. The resulting two-component spin–orbit integral matrix is by design suitable for use in perturbative calculations of spin–orbit coupling, treating SFX2C-1e wavefunctions as unperturbed states. The accuracy of the present AMF approach has been demonstrated using benchmark calculations of spin–orbit splittings for representative diatomic radicals at the equation-of-motion coupled-cluster singles and doubles level. In conclusion, to demonstrate the applicability and accuracy of the present perturbative spin–orbit scheme in calculations of challenging heavy-element containing systems, a thorough computational investigation of six low-lying electronic states of ThO+ is reported.

Authors:
 [1];  [1]
+ Show Author Affiliations
  1. Johns Hopkins Univ., Baltimore, MD (United States)
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1684918
Grant/Contract Number:  
SC0020317
Resource Type:
Accepted Manuscript
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Volume: 118; Journal Issue: 19-20; Journal ID: ISSN 0026-8976
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
97 MATHEMATICS AND COMPUTING; 74 ATOMIC AND MOLECULAR PHYSICS; Relativistic effects; relativistic quantum mechanics; spin-orbit coupling; exact two-component theory; actinide spectroscopy; mean field spin orbit approach

Citation Formats

Zhang, Chaoqun, and Cheng, Lan. Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling. United States: N. p., 2020. Web. doi:10.1080/00268976.2020.1768313.
Copy to clipboard
Zhang, Chaoqun, & Cheng, Lan. Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling. United States. https://doi.org/10.1080/00268976.2020.1768313
Copy to clipboard
Zhang, Chaoqun, and Cheng, Lan. Mon . "Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling". United States. https://doi.org/10.1080/00268976.2020.1768313. https://www.osti.gov/servlets/purl/1684918.
Copy to clipboard
@article{osti_1684918,
title = {Performance of an atomic mean-field spin–orbit approach within exact two-component theory for perturbative treatment of spin–orbit coupling},
author = {Zhang, Chaoqun and Cheng, Lan},
abstractNote = {The paper reports development of an atomic mean-field (AMF) spin–orbit approach within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e), a new relativistic quantum-chemical method for treating spin-orbit coupling in molecules. The effective one-electron spin–orbit integral matrix in the four-component representation is assembled as a direct sum of one-centre spin–orbit integral matrices with the mean-field two-electron contributions evaluated using atomic SFX2C-1e Hartree–Fock density matrices. It is then transformed into two-component representation using analytic SFX2C-1e energy derivative formulation. The resulting two-component spin–orbit integral matrix is by design suitable for use in perturbative calculations of spin–orbit coupling, treating SFX2C-1e wavefunctions as unperturbed states. The accuracy of the present AMF approach has been demonstrated using benchmark calculations of spin–orbit splittings for representative diatomic radicals at the equation-of-motion coupled-cluster singles and doubles level. In conclusion, to demonstrate the applicability and accuracy of the present perturbative spin–orbit scheme in calculations of challenging heavy-element containing systems, a thorough computational investigation of six low-lying electronic states of ThO+ is reported.},
doi = {10.1080/00268976.2020.1768313},
journal = {Molecular Physics},
number = 19-20,
volume = 118,
place = {United States},
year = {Mon May 25 00:00:00 EDT 2020},
month = {Mon May 25 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1080/00268976.2020.1768313
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

On the spin separation of algebraic two-component relativistic Hamiltonians
journal, October 2012

  • Li, Zhendong; Xiao, Yunlong; Liu, Wenjian
  • The Journal of Chemical Physics, Vol. 137, Issue 15
  • DOI: 10.1063/1.4758987

A simple scheme for the direct calculation of ionization potentials with coupled-cluster theory that exploits established excitation energy methods
journal, November 1999

  • Stanton, John F.; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 111, Issue 19
  • DOI: 10.1063/1.479673

Relativistic Hamiltonians for Chemistry: A Primer
journal, November 2011

Calculation of electric-field gradients based on higher-order generalized Douglas–Kroll transformations
journal, May 2005

  • Neese, Frank; Wolf, Alexander; Fleig, Timo
  • The Journal of Chemical Physics, Vol. 122, Issue 20
  • DOI: 10.1063/1.1904589

Spectroscopy of the ground and low-lying excited states of ThO+
journal, February 2006

  • Goncharov, Vasiliy; Heaven, Michael C.
  • The Journal of Chemical Physics, Vol. 124, Issue 6
  • DOI: 10.1063/1.2167356

Relativistic regular two-component Hamiltonians
journal, February 1996

Accurate and efficient treatment of two-electron contributions in quasirelativistic high-order Douglas-Kroll density-functional calculations
journal, November 2005

  • van Wüllen, Christoph; Michauk, Christine
  • The Journal of Chemical Physics, Vol. 123, Issue 20
  • DOI: 10.1063/1.2133731

A new relativistic theory: a relativistic scheme by eliminating small components (RESC)
journal, March 1999

Spin-orbit coupling constants from coupled-cluster response theory
journal, January 2000

  • Christiansen, Ove; Gauss, Jürgen; Schimmelpfennig, Bernd
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 5
  • DOI: 10.1039/a908995k

Fourth-order relativistic corrections to electrical first-order properties using direct perturbation theory
journal, May 2011

  • Stopkowicz, Stella; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 134, Issue 20
  • DOI: 10.1063/1.3587633

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Introduction to Relativistic Quantum Chemistry
January 2007

Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations
journal, August 2015

  • Epifanovsky, Evgeny; Klein, Kerstin; Stopkowicz, Stella
  • The Journal of Chemical Physics, Vol. 143, Issue 6
  • DOI: 10.1063/1.4927785

An atomic mean-field spin-orbit approach within exact two-component theory for a non-perturbative treatment of spin-orbit coupling
journal, April 2018

  • Liu, Junzi; Cheng, Lan
  • The Journal of Chemical Physics, Vol. 148, Issue 14
  • DOI: 10.1063/1.5023750

An infinite-order two-component relativistic Hamiltonian by a simple one-step transformation
journal, February 2007

  • Iliaš, Miroslav; Saue, Trond
  • The Journal of Chemical Physics, Vol. 126, Issue 6
  • DOI: 10.1063/1.2436882

Excitation energies with spin-orbit couplings using equation-of-motion coupled-cluster singles and doubles eigenvectors
journal, October 2017

  • Bokhan, Denis; Perera, Ajith; Trubnikov, Dmitrii N.
  • The Journal of Chemical Physics, Vol. 147, Issue 16
  • DOI: 10.1063/1.4997376

A direct product decomposition approach for symmetry exploitation in many‐body methods. I. Energy calculations
journal, March 1991

  • Stanton, John F.; Gauss, Jürgen; Watts, John D.
  • The Journal of Chemical Physics, Vol. 94, Issue 6
  • DOI: 10.1063/1.460620

A mean-field spin-orbit method applicable to correlated wavefunctions
journal, March 1996

One-Step Treatment of Spin–Orbit Coupling and Electron Correlation in Large Active Spaces
journal, December 2017

  • Mussard, Bastien; Sharma, Sandeep
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 1
  • DOI: 10.1021/acs.jctc.7b01019

Two-component methods of relativistic quantum chemistry: from the Douglas–Kroll approximation to the exact two-component formalism
journal, October 2001

The molecular mean-field approach for correlated relativistic calculations
journal, September 2009

  • Sikkema, Jetze; Visscher, Lucas; Saue, Trond
  • The Journal of Chemical Physics, Vol. 131, Issue 12
  • DOI: 10.1063/1.3239505

New Relativistic ANO Basis Sets for Transition Metal Atoms
journal, July 2005

  • Roos, Björn O.; Lindh, Roland; Malmqvist, Per-Åke
  • The Journal of Physical Chemistry A, Vol. 109, Issue 29
  • DOI: 10.1021/jp0581126

Exact two-component Hamiltonians revisited
journal, July 2009

  • Liu, Wenjian; Peng, Daoling
  • The Journal of Chemical Physics, Vol. 131, Issue 3
  • DOI: 10.1063/1.3159445

Solved and unsolved problems in relativistic quantum chemistry
journal, February 2012

Relativistic Gaussian basis sets for the elements K - Uuo
journal, January 2001

  • Faegri Jr, Knut
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 105, Issue 3
  • DOI: 10.1007/s002140000209

On the efficiency of an effective Hamiltonian in spin-orbit CI calculations
journal, April 1998

Perturbative treatment of spin-orbit coupling within spin-free exact two-component theory
journal, October 2014

  • Cheng, Lan; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 141, Issue 16
  • DOI: 10.1063/1.4897254

The fine-structure splitting of the thallium atomic ground state: LS- versus jj-coupling
journal, July 1996

Perturbative calculation of spin-orbit splittings using the equation-of-motion ionization-potential coupled-cluster ansatz
journal, November 2008

  • Klein, Kerstin; Gauss, Jürgen
  • The Journal of Chemical Physics, Vol. 129, Issue 19
  • DOI: 10.1063/1.3013199

Quasidiabatic states described by coupled-cluster theory
journal, May 2009

  • Ichino, Takatoshi; Gauss, Jürgen; Stanton, John F.
  • The Journal of Chemical Physics, Vol. 130, Issue 17
  • DOI: 10.1063/1.3127246

Inclusion of mean-field spin–orbit effects based on all-electron two-component spinors: Pilot calculations on atomic and molecular properties
journal, December 2001

  • Iliaš, Miroslav; Kellö, Vladimı́r; Visscher, Lucas
  • The Journal of Chemical Physics, Vol. 115, Issue 21
  • DOI: 10.1063/1.1413510

Quasirelativistic theory equivalent to fully relativistic theory
journal, December 2005

  • Kutzelnigg, Werner; Liu, Wenjian
  • The Journal of Chemical Physics, Vol. 123, Issue 24
  • DOI: 10.1063/1.2137315

Interfacing relativistic and nonrelativistic methods. IV. One- and two-electron scalar approximations
journal, November 2001

  • Dyall, Kenneth G.
  • The Journal of Chemical Physics, Vol. 115, Issue 20
  • DOI: 10.1063/1.1413512

Perspective: Relativistic effects
journal, April 2012

  • Autschbach, Jochen
  • The Journal of Chemical Physics, Vol. 136, Issue 15
  • DOI: 10.1063/1.3702628

An exact separation of the spin‐free and spin‐dependent terms of the Dirac–Coulomb–Breit Hamiltonian
journal, February 1994

  • Dyall, Kenneth G.
  • The Journal of Chemical Physics, Vol. 100, Issue 3
  • DOI: 10.1063/1.466508

Perturbative treatment of spin-orbit-coupling within spin-free exact two-component theory using equation-of-motion coupled-cluster methods
journal, January 2018

  • Cheng, Lan; Wang, Fan; Stanton, John F.
  • The Journal of Chemical Physics, Vol. 148, Issue 4
  • DOI: 10.1063/1.5012041

Correlation consistent basis sets for actinides. I. The Th and U atoms
journal, February 2015

  • Peterson, Kirk A.
  • The Journal of Chemical Physics, Vol. 142, Issue 7
  • DOI: 10.1063/1.4907596

Non-orthogonal spin-adaptation of coupled cluster methods: A new implementation of methods including quadruple excitations
journal, February 2015

  • Matthews, Devin A.; Stanton, John F.
  • The Journal of Chemical Physics, Vol. 142, Issue 6
  • DOI: 10.1063/1.4907278

On the spin separation of algebraic two-component relativistic Hamiltonians: Molecular properties
journal, August 2014

  • Li, Zhendong; Xiao, Yunlong; Liu, Wenjian
  • The Journal of Chemical Physics, Vol. 141, Issue 5
  • DOI: 10.1063/1.4891567

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

  • Pokhilko, Pavel; Epifanovsky, Evgeny; Krylov, Anna I.
  • The Journal of Chemical Physics, Vol. 151, Issue 3
  • DOI: 10.1063/1.5108762

A novel discrete variable representation for quantum mechanical reactive scattering via the S ‐matrix Kohn method
journal, February 1992

  • Colbert, Daniel T.; Miller, William H.
  • The Journal of Chemical Physics, Vol. 96, Issue 3
  • DOI: 10.1063/1.462100

Equation of motion coupled cluster method for electron attachment
journal, March 1995

  • Nooijen, Marcel; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 102, Issue 9
  • DOI: 10.1063/1.468592

Spin-orbit matrix elements for internally contracted multireference configuration interaction wavefunctions
journal, November 2000

  • Berning, Andreas; Schweizer, Marcus; Werner, Hans-Joachim
  • Molecular Physics, Vol. 98, Issue 21
  • DOI: 10.1080/00268970009483386

Ideas of relativistic quantum chemistry
journal, July 2010

Basis-set convergence of correlated calculations on water
journal, June 1997

  • Helgaker, Trygve; Klopper, Wim; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 106, Issue 23
  • DOI: 10.1063/1.473863

Ab initio calculations of the ${} ^2{\bi P}_{{\b 1}\over {\b 2}} \hbox{-}{} ^2{\bi P}_{{\b 3} \over {\b 2}} $ splitting in the thallium atom
journal, October 1997

  • Wahlgren, Ulf; Sjøvoll, Merethe; Fagerli, Hilde
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4
  • DOI: 10.1007/s002140050268

Communication: An accurate calculation of the S1 C2H2 cis-trans isomerization barrier height
journal, March 2016

  • Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.
  • The Journal of Chemical Physics, Vol. 144, Issue 11
  • DOI: 10.1063/1.4943865

Exact decoupling of the relativistic Fock operator
journal, January 2012

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: