Dissociation of As4 clusters following valence photoionization and 3d core excitation.

The VUV-induced photofragmentation of As4 clusters was studied using photoelectron-photoion-coincidence (PEPICO) spectroscopy. The fragmentation pathways subsequent to outer and inner valence photoionization and resonant photoexcitation were studied by examining the cationic production as a function of electron energy. In addition, regular photoelectron spectroscopy and partial ion yield absorption spectroscopy were employed. In order to enhance the weak signal from the inner valence states, resonant core 3d excitation was used in the PEPICO experiment. The fragmentation pathways were inspected with the aid of ab initio and thermochemical calculations. The many-electron effects were found to play a major role in the observed inner valence structure and resulting photofragmentation. [ABSTRACT FROM AUTHOR]