Electronic structure and photoionization dissociation studies of chlorocarbonyl trifluoromethanesulfonate, CF3SO3C(O)Cl

Abstract

Chlorocarbonyl trifluoromethanesulfonate, CF3SO3C(O)Cl, was prepared by heterogeneous reaction of gaseous ClC(O)SCl with CF3SO3Ag. The electronic structure and photoionization dissociation were investigated by HeI photoelectron spectroscopy (PES) and photoionization mass spectroscopy (PIMS). The assignments of the bands in the PES were reasonably supported by previous studies on analogous molecules, as well as the outer-valence Green’s function (OVGF) calculations. The experimental first vertical ionization potential of CF3SO3C(O)Cl was determined to be 12.36eV, which was assigned to the ionization mainly from the oxygen lone pair orbital. It shows three peaks: ClCO+ (63, 65), CF3+ (69) and CF3SO2+ (133) in the spectrum of PIMS, with the dominant features being the ClCO+ and CF3+ peaks. According to the calculated bond dissociation energies, the dissociation process was also discussed.