Photodissociation of ethylene sulfide at 193 nm: A photofragment translational spectroscopy study with VUV synchrotron radiation and ab initio calculations

被引:34
|
作者
Qi, F [1 ]
Sorkhabi, O
Suits, AG
Chien, SH
Li, WK
机构
[1] Ernest Orlando Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA
[2] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
[3] Brookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA
[4] Chinese Univ Hong Kong, Dept Chem, Shatin, Hong Kong, Peoples R China
关键词
D O I
10.1021/ja003314v
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Photodissociation of ethylene sulfide at 193 nm has been studied using photofragment translational spectroscopy and ab initio theoretical calculations. Tunable synchrotron radiation was used as a universal;out selective probe of the reaction products to reveal new aspects of the photodissociation dynamics. The channel giving S + C2H4 was found to be dominated by production of;ground-state sulfur atoms (S(P-3):S(D-1) = 1.44:1), mostly through a spin-forbidden process. The results also suggest the presence of a channel giving S(P-3) in conjunction with triplet ethylene C2H4 (B-3(tu)) and allow insight into the energy of the latter species near its equilibrium geometry, in which the two methylene groups occupy perpendicular planes, in addition, a channel leading to the production of HS with C2H2 also has been observed. Our experimental results are supported and elaborated by theoretical calculations.
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页码:148 / 161
页数:14
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