Ionic fragmentation of inner-shell excited molecules

The combination of tuneable synchrotron radiation and multicoincidence time-of-flight mass spectrometry is an effective means of studying the core-hole decay and fragmentation of inner-shell excited molecules. In addition to aiding spectral interpretation, partial ion and ion-pair yields enable both the more specific identification of fragmentation channels and the identification of site and/or state selective fragmentation processes. The power of photoelectron-photoion-photoion coincidence (PEPIPICO) and related techniques is illustrated using selected examples from recent high resolution spectroscopic and ionic fragmentation studies of PF3 and SPF3.