Correlated Dirac-Coulomb-Breit multiconfigurational self-consistent-field methods.
J Chem Phys
; 158(4): 044101, 2023 Jan 28.
Article
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| MEDLINE
| ID: mdl-36725503
ABSTRACT
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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01-internacional
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MEDLINE
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En
Revista:
J Chem Phys
Año:
2023
Tipo del documento:
Article
País de afiliación:
Estados Unidos
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EEUU
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ESTADOS UNIDOS
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ESTADOS UNIDOS DA AMERICA
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EUA
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UNITED STATES
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UNITED STATES OF AMERICA
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US
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USA