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

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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. College of William and Mary, Williamsburg, VA (United States)
  2. University of Delaware, Newark, DE (United States)
  3. Flatiron Institute, New York, NY (United States)
Publication Date:
Research Org.:
College of William and Mary, Williamsburg, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Simons Foundation
OSTI Identifier:
1979002
Alternate Identifier(s):
OSTI ID: 1838059
Grant/Contract Number:  
SC0001303
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 156; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ab-initio methods; Slater determinant; density functional theory; Monte Carlo methods; electronic correlation; relativistic effective core potentials; spin-orbit interactions; chemical bonding

Citation Formats

Eskridge, Brandon, Krakauer, Henry, Shi, Hao, and Zhang, Shiwei. Ab initio calculations in atoms, molecules, and solids, treating spin–orbit coupling and electron interaction on an equal footing. United States: N. p., 2022. Web. doi:10.1063/5.0075900.
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Eskridge, Brandon, Krakauer, Henry, Shi, Hao, & Zhang, Shiwei. Ab initio calculations in atoms, molecules, and solids, treating spin–orbit coupling and electron interaction on an equal footing. United States. https://doi.org/10.1063/5.0075900
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Eskridge, Brandon, Krakauer, Henry, Shi, Hao, and Zhang, Shiwei. Mon . "Ab initio calculations in atoms, molecules, and solids, treating spin–orbit coupling and electron interaction on an equal footing". United States. https://doi.org/10.1063/5.0075900. https://www.osti.gov/servlets/purl/1979002.
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@article{osti_1979002,
title = {Ab initio calculations in atoms, molecules, and solids, treating spin–orbit coupling and electron interaction on an equal footing},
author = {Eskridge, Brandon and Krakauer, Henry and Shi, Hao and Zhang, Shiwei},
abstractNote = {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.},
doi = {10.1063/5.0075900},
journal = {Journal of Chemical Physics},
number = 1,
volume = 156,
place = {United States},
year = {Mon Jan 03 00:00:00 EST 2022},
month = {Mon Jan 03 00:00:00 EST 2022}
}
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