The calculation of valence shell ionization potentials by the ΔSCF method

Abstract
Valence shell ionization potentials for several small molecules (HF, H2O, CH4, CO, H2S, PH3, SiH4, SO2 and F2CO) are calculated by means of ab initio ΔSCF calculations on all the valence hole states of each molecule. The results are compared with the experimental low energy photoelectron spectra. In the case of the higher energy ion states, particular attention is paid to finding practical means for obtaining convergence of the ΔSCF iterations, and numerical evidence is presented, indicating that the ΔSCF procedure provides upper bounds to the energy of such states, at least for the cases studied herein. A new procedure, the ‘ combined ΔSCF ’ method, for the determination of a common set of molecular orbitals for use in the construction of wavefunctions for a number of ion states is described.