Ionic fragmentation on ClC(O)SCl. Evidence of a highly charged molecular ion and confirmation of unusual dissociation mechanisms for halocarbonylsulfenyl chlorides.

Total and partial ion yield spectra of chlorocarbonylsulfenyl chloride, ClC(O)SCl, are studied using tunable synchrotron radiation. Multicoincidence techniques, which include photoelectron-photoion coincidence (PEPICO) and photoelectron-photoion-photoion coincidence (PEPIPICO) time-of-flight mass spectrometry, were applied to study the fragmentation dynamics around the S 2p, Cl 2p, C 1s, and O 1s ionization edges. The search for site-specific fragmentation effects showed a definite enhancement of the Cl+ signal at the Cl 2p resonance. However, fragmentation patterns of the PEPICO spectra at the various excitation energies are essentially identical. Evidence for the occurrence of the previously reported charge separation after an ion rearrangement dissociation mechanism was found. Highly charged species were observed in the multicoincidence spectra at K shell transitions, revealing the formation of a highly charged molecular ion.