Efficient evaluation of the Breit operator in the Pauli spinor basis

Sun, Shichao; Ehrman, Jordan; Sun, Qiming; Li, Xiaosong

doi:10.1063/5.0098828

Efficient evaluation of the Breit operator in the Pauli spinor basis

Journal Article · Fri Aug 12 00:00:00 EDT 2022 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0098828· OSTI ID:1979122

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Univ. of Washington, Seattle, WA (United States)
AxiomQuant Investment Management LLC, Shanghai (China)

The frequency-independent Coulomb–Breit operator gives rise to the most accurate treatment of two-electron interaction in the non-quantum-electrodynamics regime. The Breit interaction in the Coulomb gauge consists of magnetic and gauge contributions. The high computational cost of the gauge term limits the application of the Breit interaction in relativistic molecular calculations. In this work, we apply the Pauli component integral–density matrix contraction scheme for gauge interaction with a maximum spin- and component separation scheme. We also present two different computational algorithms for evaluating gauge integrals. One is the generalized Obara–Saika algorithm, where the Laplace transformation is used to transform the gauge operator into Gaussian functions and the Obara–Saika recursion is used for reducing the angular momentum. The other algorithm is the second derivative of Coulomb interaction evaluated with Rys-quadrature. This work improves the efficiency of performing Dirac–Hartree–Fock with the variational treatment of Breit interaction for molecular systems. In conclusion, we use this formalism to examine relativistic trends in the Periodic Table and analyze the relativistic two-electron interaction contributions in heavy-element complexes.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Washington, Seattle, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021100

OSTI ID:: 1979122

Alternate ID(s):: OSTI ID: 1881370

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 157; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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