Self-consistent-field calculations of core excited states

Abstract

The accuracy of core excitation energies and core electron binding energies computed within a Δself-consistent-field framework is assessed. The variational collapse of the core excited state is prevented by maintaining a singly occupied core orbital using an overlap criterion called the maximum overlap method. When applied to a wide range of small organic molecules, the resulting core excitation energies are not systematically underestimated as observed in time-dependent density functional theory and agree well with experiment. The accuracy of this approach for core excited states is illustrated by the calculation of the pre-edge features in x-ray absorption spectra of plastocyanin, which shows that accurate results can be achieved with Δself-consistent-field calculations when used in conjunction with uncontracted basis functions.N.A.B. is grateful to the ANU for a 2007 Visiting Fellowship