Valence photoionization and photoelectron-photoion coincidence (PEPICO) study of molecular LiCl and Li2Cl2

► The valence photoelectron spectra of LiCl and Li2Cl2 are recorded and re-interpreted. ► Fragmentation following ionization is explored by electron-ion coincidence. ► Ab initio calculations are used to decide which fragmentation channels are accessible. ► Formulae are provided for Franck-Condon factors pertaining to transition states.