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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4932540· OSTI ID:1469476
 [1];  [1]; ORCiD logo [1];  [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
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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.

Research Organization:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF); Gaussian, Inc., Wallingford, CT (United States)
Grant/Contract Number:
SC0006863; CHE-1265945; DGE-1256082
OSTI ID:
1469476
Alternate ID(s):
OSTI ID: 1223328
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 14; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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excitation energies
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