Free-atom—metal shifts in theM4,5N4,5N4,5Auger spectra of Ag, Cd, In, Sn, Sb, and Te

Experimental and theoretical free-atom—metal shifts have been determined for the $M_{4,5}{N}_{4,5}{N}_{4,5}$ Auger spectra of elements from ${}_{47}{}^{}{}_{}{}^{}\mathrm{Ag}$ to ${}_{52}{}^{}{}_{}{}^{}\mathrm{Te}$. The experimental shift values have been obtained either from direct measurement of free-atom—metal shifts (Ag,Cd), from measurement of molecular-vapor—metal shifts (Sb,Te) combined with semiempirically calculated free-atom Auger energies, or from comparison between calculated or measured atomic and separately measured solid-state Auger spectra (In,Sn). It is found that the free-atom—metal shifts remain almost constant through these elements in contradiction to most earlier theoretical predictions. The thermochemical model has been applied to calculate free-atom—metal shifts in the Auger spectra, and good agreement with experiment is found. The theoretical shift values have also been calculated using the self-consistent-field density-functional formalism and the results are found to agree very well with the experiment.