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Title: Communication: Hartree-Fock description of excited states of H{sub 2}

Hartree-Fock (HF) theory is most often applied to study the electronic ground states of molecular systems. However, with the advent of numerical techniques for locating higher solutions of the self-consistent field equations, it is now possible to examine the extent to which such mean-field solutions are useful approximations to electronic excited states. In this Communication, we use the maximum overlap method to locate 11 low-energy solutions of the HF equation for the H{sub 2} molecule and we find that, with only one exception, these yield surprisingly accurate models for the low-lying excited states of this molecule. This finding suggests that the HF solutions could be useful first-order approximations for correlated excited state wavefunctions.
Authors:
; ;  [1]
  1. Research School of Chemistry, Australian National University, ACT 0200 (Australia)
Publication Date:
OSTI Identifier:
22308392
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 11; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; EXCITED STATES; GROUND STATES; HARTREE-FOCK METHOD; HYDROFLUORIC ACID; HYDROGEN; MOLECULES; SELF-CONSISTENT FIELD; WAVE FUNCTIONS