Li Yu, Wang Heilong, Jiao Zhirun, Zhang Hongtao, Zhang Bingbing, Wang Xingan, Xiao Chunlei, Yang Xueming
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem A. 2024 Nov 28;128(47):10234-10239. doi: 10.1021/acs.jpca.4c06605. Epub 2024 Nov 18.
The S(D) + D → SD + D reaction is a prototype insertion chemical reaction that involves spin-orbit interactions in the exit channel. In this work, we report spin-orbit state-resolved differential cross sections (DCSs) of this reaction obtained by crossed beam experiments at collision energies of 266.2 and 206.5 cm. The DCSs of specific rovibrational states exhibit a slight preference for forward scattering. When integrated over all rotational quantum states within each spin-orbit manifold, the total angular distributions of the two manifolds show nearly forward-backward symmetry, indicating that the deep well responsible for the long-living complex-forming mechanism predominates the entire reaction dynamics. Moreover, significant spin-orbit preference was observed at rotational quantum number > 9 in the vibrationally ground state of SD products. It was also observed that SD products in the vibrationally excited state ' = 1 prefer to populate in the Π manifold, with the Π/Π ratio of 15.8 and 25.2 at collision energies of 266.2 and 206.5 cm, respectively. The experimental spin-orbit state-resolved DCSs obtained in this work will be of great importance for developing an accurate diabatic theory that includes spin-orbit interactions for this title reaction.
S(D) + D → SD + D反应是一个典型的插入化学反应,该反应在出射通道中涉及自旋 - 轨道相互作用。在本工作中,我们报告了通过交叉束实验在266.2和206.5厘米碰撞能量下获得的该反应的自旋 - 轨道态分辨微分截面(DCS)。特定振转态的DCS对前向散射表现出轻微偏好。当对每个自旋 - 轨道流形内的所有转动量子态进行积分时,两个流形的总角分布显示出近乎前后对称,这表明负责长寿命络合物形成机制的深势阱主导了整个反应动力学。此外,在SD产物的振动基态中,在转动量子数>9时观察到了显著的自旋 - 轨道偏好。还观察到,处于振动激发态' = 1的SD产物更倾向于填充在Π流形中,在266.2和206.5厘米碰撞能量下,Π/Π比分别为15.8和25.2。在本工作中获得的实验自旋 - 轨道态分辨DCS对于发展一种准确的包含该标题反应自旋 - 轨道相互作用的非绝热理论将具有重要意义。