Nonadiabatic photodissociation dynamics of thiophenol (PhSH) and deuterated thiophenol (PhSD) via the ¹ππ* state was investigated by a reduced three-dimensional (3D) quantum model based on the associated 3D diabatic potential energy surfaces constructed at the explicitly correlated multireference configuration interaction (MRCI-F12) level with the cc-pVTZ-F12 basis. The lifetimes of the low-lying vibronic S₁ states for PhSH and PhSD were calculated using a low-storage filter diagonalization method and were in reasonably good agreement with the available experimental results. The nonadiabatic effect was further examined in the photodissociation process by comparing the results in diabatic and adiabatic models. It was found that the adiabatic lifetimes were about 2–4 times shorter than the exact ones in the diabatic model for both PhSH and PhSD. More importantly, the exact ground wave function including the geometric phase (GP) possessed a node along the C–C–S–H/C–C–S–D torsional coordinate, while the node was absent when GP was not included in the adiabatic model. The node structure of the wave function was a hallmark of GP, which sheds light on the nonadiabatic photodissociation dynamics facilitated by the conical intersections.

中文翻译：

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通过绝热的影响苯硫酚解动力学¹ ππ*州

苯硫酚（加入PhSH）的非绝热光解动力学和氘代苯硫酚（PHSD）经由^1个ππ*状态被减少的三维（3D）量子基于相关联的3D绝热势能模型中研究在明确相关多引用配置相互作用表面构造（MRCI-F12）级别以cc-pVTZ-F12为基础。低洼振动S ₁的寿命PhSH和PhSD的状态是使用低存储滤波器对角化方法计算的，与可用的实验结果相当吻合。通过比较绝热和绝热模型中的结果，进一步在光解离过程中检查了非绝热效应。研究发现，对于PhSH和PhSD，绝热寿命比绝热模型中精确的寿命短2-4倍。更重要的是，包括几何相位（GP）在内的精确地波函数沿C–C–S–H / C–C–S–D扭转坐标具有一个节点，而当GP中不包含GP时该节点不存在。绝热模型。波函数的节点结构是GP的标志，它揭示了圆锥形交叉点促进的非绝热光解离动力学。