Complete breakdown of the one-electron picture of auger spectra of solids

The very broad M₄₅?N₂₃N₄₅ (3d^-1 → 4p^-14d^-1) Auger spectra for metals in the range Pd to Te arise from complete breakdown of the one-electron picture of the final state double vacancy due to 4p^-14d^-1 ? 4d^-3?f giant Coster-Kronig fluctuation and decay processes. This is an example of atomic-like effects giving rise to level shifts and broadening which are large in comparison with typical widths of d-bands in solids. The 4p^-14d^-1 two-hole spectral function can be approximated by a 4p^-1 single-hole spectral function perturbed by a static, sharp 4d^-1 hole. The resulting Auger line-shapes are different from single-hole 4p^-1 line-shapes from XPS and XES. Analogous effects also occur for double vacancies involving one or two 4s-holes.