Electronic Properties and Dissociative Photoionization of Thiocyanates. Part II. Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of Chloromethyl Thiocyanate, CH2ClSCN

LUCAS S. RODRÍGUEZ PIRANI; MARIANA GERON
ES; CARLOS O. DELLA V
EDOVA; ROSANA M. ROMANO; ADOLFO FANTONI; REINALDO CAVASSO-FILHO; CHUNPING MA; MAOFA GE; MAURICIO F. ERBEN

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2012 vol. 116 p. 231 - 241

1089-5639

A combination of photoelectron spectroscopy andsynchrotron based photoelectron photoion coincidence (PEPICO)spectra has been applied to investigate the electronic structure and thedissociative ionization of the CH2ClSCN molecule in the valenceregion. The PES is assigned with the electronic structure calculationsat the outer-valence Green’s function and symmetry adapted cluster/configuration interaction (SAC-CI) levels offer an explanation of ourexperimental results. Upon vacuum ultraviolet irradiation the lowlyingradical cation, located at 10.39 eV is formed. The molecular ion isobserved in the time-of-flight mass spectra, together with the CH2SCN+ and CH2Cl+ daughter ions. The total ion yield spectra have been measured in the S 2p and Cl 2p regions and several channels have been determined in dissociative photoionization events for the coreexcitedspecies. Thus, by using time-of-flight mass spectrometry and synchrotron radiation the relative abundances of the ionic fragments and their kinetic energy release values were obtained from both PEPICO and photoelectron photoion photoion coincidence spectra.Possible fragmentation processes are discussed and compared with that found for the related CH3SCN species.