Scalar Breit interaction for molecular calculations

Sun, Shichao; Ehrman, Jordan; Zhang, Tianyuan; Sun, Qiming; Dyall, Kenneth G.; Li, Xiaosong

doi:10.1063/5.0144359

Scalar Breit interaction for molecular calculations

Journal Article · Thu May 04 00:00:00 EDT 2023 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0144359· OSTI ID:2419711

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

Variational treatment of the Dirac–Coulomb–Gaunt or Dirac–Coulomb–Breit two-electron interaction at the Dirac–Hartree–Fock level is the starting point of high-accuracy four-component calculations of atomic and molecular systems. In this work, we introduce, for the first time, the scalar Hamiltonians derived from the Dirac–Coulomb–Gaunt and Dirac–Coulomb–Breit operators based on spin separation in the Pauli quaternion basis. While the widely used spin-free Dirac–Coulomb Hamiltonian includes only the direct Coulomb and exchange terms that resemble nonrelativistic two-electron interactions, the scalar Gaunt operator adds a scalar spin–spin term. The spin separation of the gauge operator gives rise to an additional scalar orbit-orbit interaction in the scalar Breit Hamiltonian. Benchmark calculations of Au_n (n = 2–8) show that the scalar Dirac–Coulomb–Breit Hamiltonian can capture 99.99% of the total energy with only 10% of the computational cost when real-valued arithmetic is used, compared to the full Dirac–Coulomb–Breit Hamiltonian. In conclusion, the scalar relativistic formulation developed in this work lays the theoretical foundation for the development of high-accuracy, low-cost correlated variational relativistic many-body theory.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0006863; SC0021100

OSTI ID:: 2419711

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 158; ISSN 1089-7690; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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