Ab initio calculations in atoms, molecules, and solids, treating spin-orbit coupling and electron interaction on an equal footing

Brandon Eskridge; Henry Krakauer; Hao Shi; Shiwei Zhang

doi:10.1063/5.0075900

Ab initio calculations in atoms, molecules, and solids, treating spin-orbit coupling and electron interaction on an equal footing

J Chem Phys. 2022 Jan 7;156(1):014107. doi: 10.1063/5.0075900.

Authors

Brandon Eskridge¹, Henry Krakauer¹, Hao Shi², Shiwei Zhang³

Affiliations

¹ Department of Physics, College of William and Mary, Williamsburg, Virginia 23187, USA.
² Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716, USA.
³ Center for Computational Quantum Physics, Flatiron Institute, New York, New York 10010, USA.

PMID: 34998316
DOI: 10.1063/5.0075900

Abstract

We incorporate explicit, non-perturbative treatment of spin-orbit coupling into ab initio auxiliary-field quantum Monte Carlo (AFQMC) calculations. The approach allows a general computational framework for molecular and bulk systems in which material specificity, electron correlation, and spin-orbit coupling effects can be captured accurately and on an equal footing, with favorable computational scaling vs system size. We adopt relativistic effective-core potentials that have been obtained by fitting to fully relativistic data and that have demonstrated a high degree of reliability and transferability in molecular systems. This results in a two-component spin-coupled Hamiltonian, which is then treated by generalizing the ab initio AFQMC approach. We demonstrate the method by computing the electron affinity in Pb, the bond dissociation energy in Br₂ and I₂, and solid Bi.