Relaxation processes accompanying cadmium M₄,₅N₄,₅N₄,₅Auger transitions

High resolution M 4,5 N 4,5 N 4,5 Auger spectra have been observed from solid cadmium using X-ray photoelectron spectroscopy. The multiplet structure is similar to that observed from free Cd atoms by Aksela and Aksela (see J. Phys. B, vol.7, p.1262 (1974)), but the solid state spectrum is shifted to higher kinetic energy by 12.1+or-0.7 eV. Detailed comparisons of solid state and free-atom Auger and one-electron binding energies are used to evaluate current methods of calculating Auger energies. The relationships expected between relaxation terms introduced into one- and two-step models of the Auger process are shown to hold. The failure of Hartree-Fock calculations to predict the observed multiplet splittings is shown to arise from overestimates of the F 2 and F 4 electrostatic integrals. Empirical values of these quantities are derived which, when combined with the spin-orbit coupling constant xi 4d predict the observed multiplet splittings.