Ab initio calculation of transition rates for autoionization: the Auger spectra of HF and F −

Abstract

A method for the quantitative computation angular integrated molecular Auger spectra is proposed. It combines quantum chemistry procedures for the description of the bound states involved with scattering theory for the representation of the scattering states. The bound states are described by configuration-interaction (CI) wavefunctions; the scattering problem is solved by a Green operator formalism. The method is illustrated by computing the Auger spectra of hydrogen fluoride and because we want to investigate the molecular effects, the isoelectronic fluoride ion.