Outermost and Inner-Shell Electronic Properties of ClC(O)SCH2CH3 Studied Using HeI Photoelectron Spectroscopy and Synchrotron Radiation

LUCAS S. RODRíGUEZ PIRANI; MAURICIO F. ERBEN; MARIANA GERONéS; CHUNPING MA; MAOFA GE; ROSANA M. ROMANO,; REINALDO L. CAVASSO FILHO; CARLOS O. DELLA VéDOVA

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2011 vol. 115 p. 5307 - 5318

1089-5639

1-Abstract               A study of valence electronic properties of S-ethyl chlorothioformate (S-ethyl chloromethanethioate), ClC(O)SCH2CH3, using a combined approach that includes the use of HeI photoelectron spectra (PES) and synchrotron radiation is presented. Moreover, the photon impact excitation and dissociation dynamics of ClC(O)SCH2CH3 excited at the S 2p and Cl 2p levels are elucidated by analyzing the Total Ion Yield spectra (TIY) and time-of-flight mass spectra acquired in the multi-coincidence mode [Photoelectron-Photoion-Coincidence (PEPICO) and Photoelectron-Photoion- Photoion-Coincidence (PEPIPICO)]. The HeI photoelectron spectrum is dominated by features associated with lone-pair electrons from the ClC(O)S? group, the HOMO at 9.84 eV being assigned to the nð(S) sulfur lone-pair orbital. While the formation of C2H5+ ion dominates the fragmentation in the valence energy region, the most abundant ion formed in both S and Cl 2p energy ranges is C2H3+. The comparison with related XC(O)SR (X= H, F, Cl and R= ?CH3, ?C2H5) species reveals the importance of the alkyl chain on the photodissociation behavior of S-alkyl (halo)thioformates.