The calculation of molecular and cluster auger spectra

The work of Asaad and Burhop and of Shirley on atoms is Shown to form the basis of a useful theory for the analysis of molecular core-valence-valence Auger spectra. If the static relaxation term of Shirley is neglected, the theory requires only a single SCF calculation on the neutral molecule. Since this approximation seems justified for the class of itinerant holes, the theory not only pemits the interpretation of the spectra of molecules considerably larger than previously analyzed, but potentially the spectra of chemisorbed molecules from cluster calculations. Theory and experiment are compared for the carbon KW spectra ofCH₄, C₂H₂, C₂H₄ and CH₃OH.