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

RODRIGUEZ PIRANI, LUCAS SEBASTIÁN; GERONÉS, MARIANA; DELLA VÉDOVA, CARLOS OMAR; ROMANO, ROSANA MARIEL; FANTONI, ADOLFO; CAVASSO FILHO, REINALDO; CHUNPING, MA; GE, MAO-FA; ERBEN, MAURICIO FEDERICO

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

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

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 analyzingthe 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+ 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+. 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.