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.
Skip Nav Destination
CHORUS
Article navigation
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
Search for other works by this author on:
Lixin Lu
;
Lixin Lu
(Data curation, Formal analysis, Investigation, Methodology, Software)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
Search for other works by this author on:
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
Search for other works by this author on:
Kirill D. Shumilov;
Kirill D. Shumilov
(Data curation, Formal analysis)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
Search for other works by this author on:
Shichao Sun
;
Shichao Sun
(Methodology)
1
Department of Chemistry, University of Washington
, Seattle, Washington 98195, USA
Search for other works by this author on:
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
Search for other works by this author on:
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
Search for other works by this author on:
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
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Freezing point depression of salt aqueous solutions using the Madrid-2019 model
Cintia P. Lamas, Carlos Vega, et al.
Related Content
Four-component full configuration interaction quantum Monte Carlo for relativistic correlated electron problems
J. Chem. Phys. (November 2020)
Efficient evaluation of the Breit operator in the Pauli spinor basis
J. Chem. Phys. (August 2022)
Scalar Breit interaction for molecular calculations
J. Chem. Phys. (May 2023)
Breit corrections to individual atomic and molecular orbital energies
J. Chem. Phys. (January 2018)