Efficient Four-Component Dirac–Coulomb–Gaunt Hartree–Fock in the Pauli Spinor Representation

Sun, Shichao; Stetina, Torin F.; Zhang, Tianyuan; Hu, Hang; Valeev, Edward F.; Sun, Qiming; Li, Xiaosong

doi:10.1021/acs.jctc.1c00137

Title: Efficient Four-Component Dirac–Coulomb–Gaunt Hartree–Fock in the Pauli Spinor Representation

Journal Article · Mon May 24 00:00:00 EDT 2021 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.1c00137· OSTI ID:1870641

^[1];

^[1]; Zhang, Tianyuan ^[1]; Hu, Hang ^[1];

^[2]; Sun, Qiming ^[3];

^[1]

Univ. of Washington, Seattle, WA (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
AxiomQuant Investment Management LLC, Shanghai (China)

Four-component Dirac Hartree--Fock is an accurate mean-field method for treating molecular systems where relativistic effects are important. However, the computational cost and complexity of the two-electron interaction makes this method less common, even though we can consider the Dirac Hartree--Fock Hamiltonian the ``ground truth" of electronic structure, barring explicit quantum-electrodynamical effects. Being able to calculate these effects is then vital to the design of lower scaling methods for accurate predictions in computational spectroscopy and properties of heavy element complexes that must include relativistic effects for even qualitative accuracy. In this work, we present a Pauli quaternion formalism of maximal component- and spin-separation for computing the Dirac-Coulomb-Gaunt Hartree-Fock ground state, with a minimal floating-point-operation count algorithm. Furthermore, this approach also allows one to explicitly separate different spin physics from the two-body interactions, such as spin-free, spin-orbit, and the spin-spin contributions. Additionally, we use this formalism to examine relativistic trends in the periodic table, and analyze the basis set dependence of atomic gold and gold dimer systems.

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

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

Grant/Contract Number:: SC0021100

OSTI ID:: 1870641

Journal Information:: Journal of Chemical Theory and Computation, Vol. 17, Issue 6; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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