The fully correlated frequency-independent Dirac–Coulomb–Breit Hamiltonian provides the most accurate description of electron–electron interaction before going to a genuine relativistic quantum electrodynamics theory of many-electron systems. In this work, we introduce a correlated Dirac–Coulomb–Breit multiconfigurational self-consistent-field method within the frameworks of complete active space and density matrix renormalization group. In this approach, the Dirac–Coulomb–Breit Hamiltonian is included variationally in both the mean-field and correlated electron treatment. We also analyze the importance of the Breit operator in electron correlation and the rotation between the positive- and negative-orbital space in the no-virtual-pair approximation. Atomic fine-structure splittings and lanthanide contraction in diatomic fluorides are used as benchmark studies to understand the contribution from the Breit correlation.
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28 January 2023
Research Article|
January 23 2023
Correlated Dirac–Coulomb–Breit multiconfigurational self-consistent-field methods
Chad E. Hoyer
;
Chad E. Hoyer
(Data curation, Formal analysis, Investigation, Methodology, Visualization, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
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Lixin Lu
;
Lixin Lu
(Data curation, Formal analysis, Investigation, Methodology, Software)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
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Hang Hu;
Hang Hu
(Data curation, Formal analysis, Methodology, Software, Validation, Visualization, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
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Kirill D. Shumilov;
Kirill D. Shumilov
(Data curation, Formal analysis)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
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Shichao Sun
;
Shichao Sun
(Methodology)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
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Stefan Knecht
;
Stefan Knecht
a)
(Formal analysis, Methodology, Software, Supervision, Validation, Writing – original draft, Writing – review & editing)
2
Algorithmiq Ltd.
, Kanavakatu 3C, FI-00160 Helsinki, Finland
3
ETH Zürich, Laboratory for Physical Chemistry
, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland
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Xiaosong Li
Xiaosong Li
a)
(Conceptualization, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Software, Supervision, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
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J. Chem. Phys. 158, 044101 (2023)
Article history
Received:
November 05 2022
Accepted:
December 29 2022
Citation
Chad E. Hoyer, Lixin Lu, Hang Hu, Kirill D. Shumilov, Shichao Sun, Stefan Knecht, Xiaosong Li; Correlated Dirac–Coulomb–Breit multiconfigurational self-consistent-field methods. J. Chem. Phys. 28 January 2023; 158 (4): 044101. https://doi.org/10.1063/5.0133741
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