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

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 123, 期 1, 页码 148-161

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AMER CHEMICAL SOC
DOI: 10.1021/ja003314v

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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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