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

Año: 2011 vol. 115 p. 5308 - 5318

1089-5639

A study of valence electronic properties of S-ethyl chlorothioformate (S-ethyl chloromethanethioate), ClC(O)SCH2CH3, using 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 (TIY) spectra and time-of-flight mass spectra acquired in multicoincidence 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 nπ(S) sulfur lone-pair orbital.Whereas the formation of C2H5 þ ion dominates the fragmentation in the valence energy region, the most abundant ion formed in both the S and Cl 2p energy ranges is C2H3 þ. Comparison with related XC(O)SR (X = H, F, Cl and R =—CH3,—C2H5) species reveals the impact of the alkyl chain on the photodissociation behavior of S-alkyl (halo)thioformates.