The Calculation of Atomic and Molecular Electron Binding Energies

Abstract

Interest in accurate theoretical determination of electron binding energies has grown with the experimental advances in the field of photoelectron spectrometry. Much early work [1] on ionization potentials, photoionization cross sections, chemical shifts etc. relied on semiempirical models. It was also recognized early [2] that ground state Hartree-Fock ab-initio orbital energies (according to Koopmans’ theorem) can with some success be used as measures of valence electron binding energies, while core ionization energies are rather poorly represented in this manner.