TY - JOUR
T1 - Communication
T2 - Hartree-Fock description of excited states of H2
AU - Barca, Giuseppe M.J.
AU - Gilbert, Andrew T.B.
AU - Gill, Peter M.W.
N1 - Publisher Copyright:
© 2014 AIP Publishing LLC.
PY - 2014/9/21
Y1 - 2014/9/21
N2 - 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 H2molecule 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.
AB - 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 H2molecule 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.
UR - http://www.scopus.com/inward/record.url?scp=84907482396&partnerID=8YFLogxK
U2 - 10.1063/1.4896182
DO - 10.1063/1.4896182
M3 - Article
SN - 0021-9606
VL - 141
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 11
M1 - 111104
ER -