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首页> 外文期刊>The Journal of Chemical Physics >Correlated Dirac-Coulomb-Breit multiconfigurational self-consistent-field methods
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Correlated Dirac-Coulomb-Breit multiconfigurational self-consistent-field methods

机译:Correlated Dirac-Coulomb-Breit multiconfigurational self-consistent-field methods

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摘要

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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