Theoretical Chemistry Accounts

, Volume 99, Issue 2, pp 83–87

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

  • Peter Politzer
  • Fakher Abu-Awwad
Regular article

DOI: 10.1007/s002140050307

Cite this article as:
Politzer, P. & Abu-Awwad, F. Theor Chem Acc (1998) 99: 83. doi:10.1007/s002140050307


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.

Key words: Hartree-Fock orbital energiesKohn-Sham orbital energiesIonization potentials

Copyright information

© Springer-Verlag Berlin Heidelberg 1998

Authors and Affiliations

  • Peter Politzer
    • 1
  • Fakher Abu-Awwad
    • 1
  1. 1.University of New Orleans, Department of Chemistry, New Orleans, LA 70148, USAUS