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:
-
- 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. https://doi.org/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. https://doi.org/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 = {Fri Oct 09 00:00:00 EDT 2015},
month = {Fri Oct 09 00:00:00 EDT 2015}
}
Web of Science
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Works referencing / citing this record:
Embedding non-collinear two-component electronic structure in a collinear quantum environment
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