Interplay of atomic and solid-state effects in inner-shell-resonant photoelectron spectra

We report photoelectron spectra of metal chlorides excited in the vicinity of the chlorine 2p absorption edge. The spectra of RbCl, which has a narrow valence band, exhibit a strong resonance behavior. Hartree-Fock calculations show that the absorption final states are the atomiclike Frenkel excitons. Their decay is dominated by the Anger process where the final-state 4s and 3d electrons behave as spectators. In the sequence of chlorides with increasing width of the valence band the atomiclike resonance effects are continuously replaced by the bandlike shape of the spectra.