Ab initio Calculations in Atoms, Molecules, and Solids, Treating Spin-Orbit Coupling and Electron Interaction on Equal Footing
arXiv:2110.10201 · 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 materials specificity, electron correlation, and spin-orbit coupling effects can be captured accurately and on equal footing, with favorable computational scaling versus system size. We adopt relativistic effective-core potentials which have been obtained by fitting to fully relativistic data and which have demonstrated a high degree of reliability and transferability in molecular systems. This results in a 2-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 Br and I, and solid Bi.
arXiv comment26 pages, 4 figures, submitted to The Journal of Chemical Physics
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