Published in

American Institute of Physics, The Journal of Chemical Physics, 11(141), p. 111104

DOI: 10.1063/1.4896182

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Communication: Hartree-Fock description of excited states of H2

Journal article published in 2014 by Giuseppe M. J. Barca ORCID, Andrew T. B. Gilbert, Peter M. W. Gill
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

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 H2 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.