Qi F, Sorkhabi O, Suits A G, Chien S H, Li W K
Chemical Sciences Division, Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
J Am Chem Soc. 2001 Jan 10;123(1):148-61. doi: 10.1021/ja003314v.
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 but 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(3P):S(1D) = 1.44:1), mostly through a spin-forbidden process. The results also suggest the presence of a channel giving S(3P) in conjunction with triplet ethylene C2H4 (3B(1u)) 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 H2S with C2H2 also has been observed. Our experimental results are supported and elaborated by theoretical calculations.
利用光碎片平移光谱和从头算理论计算研究了193 nm波长下乙硫醚的光解离。可调谐同步辐射用作反应产物的通用但选择性探针，以揭示光解离动力学的新方面。发现生成S + C2H4的通道主要由基态硫原子（S(3P):S(1D) = 1.44:1）的产生主导，主要通过自旋禁阻过程。结果还表明存在一个通道，该通道生成S(3P)并伴有三重态乙烯C2H4 (3B(1u))，并能深入了解后者在其平衡几何构型附近的能量，其中两个亚甲基占据相互垂直的平面。此外，还观察到一个生成H2S和C2H2的通道。我们的实验结果得到了理论计算的支持和阐述。
