title: Outermost and inner-shell electronic properties of ClC(O)SCH2CH3 studied using HeI photoelectron spectroscopy and synchrotron radiation.
abstract: A study of valence electronic properties of S-ethyl chlorothioformate (S-ethyl chloromethanethioate), ClC(O)SCH(2)CH(3), using HeI photoelectron spectra (PES) and synchrotron radiation is presented. Moreover, the photon impact excitation and dissociation dynamics of ClC(O)SCH(2)CH(3) 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 n(π)(S) sulfur lone-pair orbital. Whereas the formation of C(2)H(5)(+) ion dominates the fragmentation in the valence energy region, the most abundant ion formed in both the S and Cl 2p energy ranges is C(2)H(3)(+). Comparison with related XC(O)SR (X = H, F, Cl and R = -CH(3), -C(2)H(5)) species reveals the impact of the alkyl chain on the photodissociation behavior of S-alkyl (halo)thioformates.
authors.affiliation: CEQUINOR (CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C. C. 962 (1900) La Plata, República Argentina.
authors.forename: Lucas S Rodríguez
authors.initials: LS
authors.lastname: Pirani
authors.forename: Mauricio F
authors.initials: MF
authors.lastname: Erben
authors.forename: Mariana
authors.initials: M
authors.lastname: Geronés
authors.forename: Chunping
authors.initials: C
authors.lastname: Ma
authors.forename: Maofa
authors.initials: M
authors.lastname: Ge
authors.forename: Rosana M
authors.initials: RM
authors.lastname: Romano
authors.forename: Reinaldo L Cavasso
authors.initials: RL
authors.lastname: Filho
authors.forename: Carlos O
authors.initials: CO
authors.lastname: Della Védova