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Title: Approximate singly excited states from a two-component Hartree-Fock reference

Abstract

For many molecules, relaxing the spin symmetry constraint on the wave function results in the lowest energy mean-field solution. The two-component Hartree-Fock (2cHF) method relaxes all spin symmetry constraints, and the wave function is no longer an eigenfunction of the total spin, spin projection, or time-reversal symmetry operators. For ground state energies, 2cHF is a superior mean-field method for describing spin-frustrated molecules. For excited states, the utility of 2cHF is uncertain. Here, we implement the 2cHF extensions of two single-reference excited state methods, the two-component configuration interaction singles and time-dependent Hartree-Fock. In this, we compare the results to the analogous methods based off of the unrestricted Hartree-Fock approximation, as well as the full configuration interaction for three small molecules with distinct 2cHF solutions, and discuss the nature of the 2cHF excited state solutions.

Authors:
 [1];  [1]; ORCiD logo [1];  [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); Gaussian, Inc., Wallingford, CT (United States)
OSTI Identifier:
1469476
Alternate Identifier(s):
OSTI ID: 1223328
Grant/Contract Number:  
SC0006863; CHE-1265945; DGE-1256082
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 14; 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; particle symmetry; slater determinant; functional equations; full configuration interaction; oscillator strengths; chemical elements; excitation energies; zero point energy; self consistent field methods; leptons

Citation Formats

Goings, Joshua J., Ding, Feizhi, Davidson, Ernest R., and Li, Xiaosong. Approximate singly excited states from a two-component Hartree-Fock reference. United States: N. p., 2015. Web. doi:10.1063/1.4932540.
Goings, Joshua J., Ding, Feizhi, Davidson, Ernest R., & Li, Xiaosong. Approximate singly excited states from a two-component Hartree-Fock reference. United States. doi:10.1063/1.4932540.
Goings, Joshua J., Ding, Feizhi, Davidson, Ernest R., and Li, Xiaosong. Fri . "Approximate singly excited states from a two-component Hartree-Fock reference". United States. doi:10.1063/1.4932540. https://www.osti.gov/servlets/purl/1469476.
@article{osti_1469476,
title = {Approximate singly excited states from a two-component Hartree-Fock reference},
author = {Goings, Joshua J. and Ding, Feizhi and Davidson, Ernest R. and Li, Xiaosong},
abstractNote = {For many molecules, relaxing the spin symmetry constraint on the wave function results in the lowest energy mean-field solution. The two-component Hartree-Fock (2cHF) method relaxes all spin symmetry constraints, and the wave function is no longer an eigenfunction of the total spin, spin projection, or time-reversal symmetry operators. For ground state energies, 2cHF is a superior mean-field method for describing spin-frustrated molecules. For excited states, the utility of 2cHF is uncertain. Here, we implement the 2cHF extensions of two single-reference excited state methods, the two-component configuration interaction singles and time-dependent Hartree-Fock. In this, we compare the results to the analogous methods based off of the unrestricted Hartree-Fock approximation, as well as the full configuration interaction for three small molecules with distinct 2cHF solutions, and discuss the nature of the 2cHF excited state solutions.},
doi = {10.1063/1.4932540},
journal = {Journal of Chemical Physics},
number = 14,
volume = 143,
place = {United States},
year = {2015},
month = {10}
}

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