Outermost and inner-shell electronic properties of ClC(O)SCH2CH3 studied using HeI photoelectron spectroscopy and synchrotron radiation.
| Autor: | Pirani LS; CEQUINOR (CONICET-UNLP), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C. C. 962 (1900) La Plata, República Argentina., Erben MF, Geronés M, Ma C, Ge M, Romano RM, Filho RL, Della Védova CO |
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| Jazyk: | angličtina |
| Zdroj: | The journal of physical chemistry. A [J Phys Chem A] 2011 Jun 02; Vol. 115 (21), pp. 5307-18. Date of Electronic Publication: 2011 May 10. |
| DOI: | 10.1021/jp112182x |
| Abstrakt: | 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. (© 2011 American Chemical Society) |
| Databáze: | MEDLINE |
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