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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation Dynamics of Thiophenol-d1: The Nature of Excited Electronic States alongthe S—D Bond Dissociation Coordinate
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Photodissociation Dynamics of Thiophenol-d1: The Nature of Excited Electronic States alongthe S—D Bond Dissociation Coordinate

机译：硫酚-d1的光解离动力学：沿着SD键解离坐标的激发电子态的性质

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摘要

The S-D bond dissociation dynamics of thiophenol-d_1 (C_6H_5SD) pumped at 266, 243, and 224 nm are examinedusing the velocity map ion imaging technique. At both 266 and 243 nm, distinct peaks associated with X andA states of the phenylthiyl radical (C_6H_5S ) are observed in theD~+image at high and low kinetic energyregions, respectively. The partitioning of the available energy into the vibrational energy of the phenylthiylradical is found to be enhanced much more strongly at 266 nm compared to that at 243 nm. This indicatesthat the ππ~*electronic excitation at 266 nm is accompanied by significant vibrational excitation. Given therelatively large anisotropy parameter of -0.6, the S -D dissociation at 266 nm is prompt and should involvethe efficient coupling to the upper-lying n_πσ~* repulsive potential energy surface. The optical excitation ofthiophenol at 224 nm is tentatively assigned to the πσ~*transition, which leads to the fast dissociation on therepulsive potential energy surface along the S-D coordinate. The nature of the electronic transitions associatedwith UV absorption bands is investigated with high-level ab initio calculations. Excitations to different electronicstates of thiophenol result in unique branching ratios and vibrational excitations for the fragment of thephenylthiyl radical in the two lowest electronic states.
机译：使用速度图离子成像技术检查了在266、243和224 nm泵浦的硫酚-d_1（C_6H_5SD）的S-D键解离动力学。在266 nm和243 nm处，分别在高动能区和低动能区的D〜+图像中观察到与苯硫基自由基（C_6H_5S）的X和A状态相关的明显峰。与243 nm相比，发现在266 nm处将可用能量分配到苯基噻吩基自由基的振动能中的作用大大增强。这表明在266nm处的ππ*电子激发伴随着显着的振动激发。考虑到相对较大的各向异性参数-0.6，在266 nm处的S -D离解是迅速的，应该涉及到与上层n_πσ〜*排斥势能表面的有效耦合。苯硫酚在224 nm处的光激发被暂时分配给πσ〜*跃迁，这导致沿S-D坐标在势能能表面上快速解离。通过高水平的从头算计算研究了与紫外线吸收带相关的电子跃迁的性质。硫酚的不同电子态的激发导致两个最低电子态的苯硫基自由基片段具有独特的支化比和振动激发。

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