Probing dissociative molecular dications by mapping vibrational wave functions

We present high-resolution photoelectron-Auger-electron coincidence spectra of methane (CH{sub 4}). Since the vibrational structure in the photoelectron spectrum is resolved, the Auger spectra corresponding to different vibrational levels can be separated. The seven final states of CH{sub 4}{sup 2+} are either dissociative or metastable, but in any case are populated in a repulsive part of their potential-energy curve via the Auger decay. The Auger line shapes can therefore be obtained by mapping the vibrational wave functions of the core-hole state into energy space. We have implemented this connection in the data analysis. By simultaneously fitting the different Auger spectra, detailed information on the energies of the dicationic states and their repulsive potential-energy curves is derived.