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Published in

American Institute of Physics, The Journal of Chemical Physics, 4(158), p. 044101, 2023

DOI: 10.1063/5.0133741

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Correlated Dirac–Coulomb–Breit multiconfigurational self-consistent-field methods

This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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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.