Localized vs delocalized description of photoelectron spectra

Abstract

A model calculation is presented to investigate the conditions under which an excitation of a molecule or solid should be treated in a symmetry restricted or localized manner. The three important quantities in the model, the hole delocalization energy, the response time of the polarizable medium, and the interaction between the hole and the polarizable medium are included as variables. The exact solution is compared to approximations, and ranges of the three above‐mentioned quantities are found for which the symmetry restricted or localized solutions yield the best results. It is found that the localized solutions with symmetrization afterwards yield the best results for a surprisingly large range of the three interactions and seems to be the better solution even for describing valence orbital photoelectron spectra