Electronic Properties of FC(O)SCH2CH3. A Combined Helium(I) Photoelectron Spectroscopy and Synchrotron Radiation Study

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• 作者：Lucas S. Rodr铆guez Pirani ; Mauricio F. Erben ; Mariana Geron茅s ; Rosana M. Romano ; Reinaldo L. Cavasso Filho ; Chunping Ma ; Maofa Ge ; Carlos O. Della V茅dova
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：August 7, 2014
• 年：2014
• 卷：118
• 期：31
• 页码：5950-5960
• 全文大小：542K
• ISSN：1520-5215

文摘

The valence electronic properties of S-ethyl flouromethanethioate (S-ethyl fluoromethsanethioate), FC(O)SCH₂CH₃, were investigated by means of He(I) photoelectron spectroscopy in conjunction with the analysis of the photofragmentation products determined by PEPICO (phtoelectron-photoion-coincidence) by using synchrotron radiation in the 11.1鈥?1.6 eV photon energy range. The first band observed at 10.28 eV in the HeI photoelectron spectrum can be assigned with confidence to the ionization process from the HOMO [n_蟺(S) orbital], which is described as a lone pair formally localized on the sulfur atom, in agreement with quantum chemical calculations using the outer valence Green function method [OVGF/6-311++G (d,p)]. One of the most important fragmentation channels also observed in the valence region corresponds to the decarbonylation process yielding the [M鈥揅O]^路+ ion, which is clearly observed at m/z = 80. Moreover, S 2p and S 2s absorption edges have been examined by measuring the total ion yield spectra in the 160鈥?40 eV region using variable synchrotron radiation. The dynamic of ionic fragmentation following the Auger electronic decay has been evaluated with the help of the PEPIPICO (photoion鈥損hotoion鈥損hotoelectron鈥揷oincidence spectra) technique.