, Volume 99, Issue 2, pp 83-87

A comparative analysis of Hartree-Fock and Kohn-Sham orbital energies

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Hartree-Fock and Kohn-Sham orbital energies, the latter computed with several different exchange/correlation functionals, are compared and analyzed for 12 molecules. The Kohn-Sham energies differ significantly from experimental ionization energies, but by amounts that are, for a given molecule and exchange/correlation functional, roughly the same for all of the valence orbitals. With the exchange/correlation functionals used, the energy of the highest occupied Kohn-Sham orbital does not approximate the corresponding ionization potential any better than do the other orbital energies.

Received: 24 October 1997 / Accepted 31 October 1997