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Title: General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions

Abstract

Standard implementations of nonrelativistic excited-state calculations compute only one component of spin multiplets (i.e., Ms = 0 triplets); however, matrix elements for all components are necessary for deriving spin-dependent experimental observables. Wigner–Eckart’s theorem allows one to circumvent explicit calculations of all multiplet components. We generate all other spin–orbit matrix elements by applying Wigner–Eckart’s theorem to a reduced one-particle transition density matrix computed for a single multiplet component. In addition to computational efficiency, this approach also resolves the phase issue arising within Born–Oppenheimer’s separation of nuclear and electronic degrees of freedom. A general formalism and its application to the calculation of spin–orbit couplings using equation-of-motion coupled-cluster wave functions are presented. The two-electron contributions are included via the mean-field spin–orbit treatment. Intrinsic issues of constructing spin–orbit mean-field operators for open-shell references are discussed, and a resolution is proposed. The method is benchmarked by using several radicals and diradicals. The merits of the approach are illustrated by a calculation of the barrier for spin inversion in a high-spin tris(pyrrolylmethyl)amine Fe(II) complex.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
  1. Univ. of Southern California, Los Angeles, CA (United States)
  2. Q-Chem, Inc., Pleasanton, CA (United States)
  3. Univ. of Southern California, Los Angeles, CA (United States); Johannes Gutenberg Univ., Mainz (Germany)
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1613024
Alternate Identifier(s):
OSTI ID: 1542533
Grant/Contract Number:  
SC0018910
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Chemistry; Physics; Magnetic materials; Relativistic effects; Transition metals; Coupled-cluster methods; Wigner-Eckart theorem; Density-matrix

Citation Formats

Pokhilko, Pavel, Epifanovsky, Evgeny, and Krylov, Anna I. General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5108762.
Pokhilko, Pavel, Epifanovsky, Evgeny, & Krylov, Anna I. General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions. United States. https://doi.org/10.1063/1.5108762
Pokhilko, Pavel, Epifanovsky, Evgeny, and Krylov, Anna I. Mon . "General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions". United States. https://doi.org/10.1063/1.5108762. https://www.osti.gov/servlets/purl/1613024.
@article{osti_1613024,
title = {General framework for calculating spin–orbit couplings using spinless one-particle density matrices: Theory and application to the equation-of-motion coupled-cluster wave functions},
author = {Pokhilko, Pavel and Epifanovsky, Evgeny and Krylov, Anna I.},
abstractNote = {Standard implementations of nonrelativistic excited-state calculations compute only one component of spin multiplets (i.e., Ms = 0 triplets); however, matrix elements for all components are necessary for deriving spin-dependent experimental observables. Wigner–Eckart’s theorem allows one to circumvent explicit calculations of all multiplet components. We generate all other spin–orbit matrix elements by applying Wigner–Eckart’s theorem to a reduced one-particle transition density matrix computed for a single multiplet component. In addition to computational efficiency, this approach also resolves the phase issue arising within Born–Oppenheimer’s separation of nuclear and electronic degrees of freedom. A general formalism and its application to the calculation of spin–orbit couplings using equation-of-motion coupled-cluster wave functions are presented. The two-electron contributions are included via the mean-field spin–orbit treatment. Intrinsic issues of constructing spin–orbit mean-field operators for open-shell references are discussed, and a resolution is proposed. The method is benchmarked by using several radicals and diradicals. The merits of the approach are illustrated by a calculation of the barrier for spin inversion in a high-spin tris(pyrrolylmethyl)amine Fe(II) complex.},
doi = {10.1063/1.5108762},
journal = {Journal of Chemical Physics},
number = 3,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}

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Cited by: 9 works
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