对撞能量为 266.2 和 206.5 cm-1 时 S(1D) + D2 → SD(2Π3/2,1/2) + D 反应的实验自旋轨道态分辨差分截面。

IF 2.7 2区 化学 Q3 CHEMISTRY, PHYSICAL The Journal of Physical Chemistry A Pub Date : 2024-11-28 Epub Date: 2024-11-18 DOI:10.1021/acs.jpca.4c06605
Yu Li, Heilong Wang, Zhirun Jiao, Hongtao Zhang, Bingbing Zhang, Xingan Wang, Chunlei Xiao, Xueming Yang
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引用次数: 0

摘要

S(1D) + D2 → SD + D 反应是一种原型插入化学反应,涉及出口通道中的自旋轨道相互作用。在这项工作中,我们报告了在碰撞能量为 266.2 和 206.5 cm-1 时通过交叉光束实验获得的该反应的自旋轨道态分辨微分截面(DCS)。特定旋转振动态的 DCS 稍微偏向于正向散射。对每个自旋轨道流形内的所有旋转量子态进行积分后,两个流形的总角分布几乎呈现出前后对称性,这表明负责长寿命复合物形成机制的深井在整个反应动力学中占主导地位。此外,在 SD 产物的振动基态中,旋转量子数 N > 9 时观察到了明显的自旋轨道偏好。还观察到振动激发态 v' = 1 的 SD 产物更倾向于在 2Π3/2 流形中填充,在碰撞能量为 266.2 和 206.5 cm-1 时,2Π3/2/2Π1/2 比率分别为 15.8 和 25.2。这项工作中获得的实验自旋轨道态分辨 DCS 对于为这一标题反应建立包含自旋轨道相互作用的精确二重态理论具有重要意义。
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Experimental Spin-Orbit State-Resolved Differential Cross Sections of the S(1D) + D2 → SD(2Π3/2,1/2) + D Reaction at Collision Energies of 266.2 and 206.5 cm-1.

The S(1D) + D2 → 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-1. 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 N > 9 in the vibrationally ground state of SD products. It was also observed that SD products in the vibrationally excited state v' = 1 prefer to populate in the 2Π3/2 manifold, with the 2Π3/2/2Π1/2 ratio of 15.8 and 25.2 at collision energies of 266.2 and 206.5 cm-1, 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.

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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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