Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2007-08-23

Dissociative photoionization of methoxycarbonylsulfenyl chloride, CH3OC(O)SCl, following sulfur 2p, chlorine 2p, and oxygen 1s excitations.

Mauricio F Erben, Mariana Geronés, Rosana M Romano, Carlos O Della Védova

Index: J. Phys. Chem. A 111(33) , 8062-71, (2007)

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Abstract

Total ion yield spectra and photoinduced fragmentations following S 2p, Cl 2p, and O 1s inner shell excitations of methoxycarbonylsulfenyl chloride, CH(3)OC(O)SCl, have been studied in the gaseous phase by using synchrotron radiation and multicoincidence techniques, which include photoelectron-photoion coincidence (PEPICO) and photoelectron-photoion-photoion coincidence (PEPIPICO) time-of-flight (TOF) mass spectrometry. According to the analysis of the partial ion yield spectra the S+ ion signal shows a steep enhancement near the S 2p resonance, which could represent an evidence of state-specific fragmentations promoted by electronic excitations from the S 2p to vacant orbitals with strong antibonding character mainly located at the sulfur atom. The dissociation dynamics for selected PEPIPICO islands have been discussed. Fragmentation channels that involve the extrusion of H+ and CH(x)+ (x = 0, 1, 2, 3) fragments have been predominantly observed for dissociation of doubly charged CH(3)OC(O)SCl(2+).