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

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• 作者：Lucas S. Rodri虂guez Pirani ; Mauricio F. Erben ; Mariana Gerone虂s ; Chunping Ma ; Maofa Ge ; Rosana M. Romano ; Reinaldo L. Cavasso Filho ; Carlos O. Della Ve虂dova
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：June 2, 2011
• 年：2011
• 卷：115
• 期：21
• 页码：5307-5318
• 全文大小：1147K
• 年卷期：v.115,no.21(June 2, 2011)
• ISSN：1520-5215

文摘

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鈥損hotoion coincidence (PEPICO) and photoelectron鈥損hotoion鈥損hotoion coincidence (PEPIPICO)]. The HeI photoelectron spectrum is dominated by features associated with lone-pair electrons from the ClC(O)S鈥?group, the HOMO at 9.84 eV being assigned to the n_蟺(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 = 鈥擟H₃, 鈥擟₂H₅) species reveals the impact of the alkyl chain on the photodissociation behavior of S-alkyl (halo)thioformates.