Xu Xin, Chen Jun, Liu Shu, Zhang Dong H
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Phys Chem A. 2023 Nov 16;127(45):9513-9519. doi: 10.1021/acs.jpca.3c05844. Epub 2023 Nov 3.
We utilized the time-dependent wave packet approach to compute the first full-dimensional (6D) state-to-state differential cross sections (DCSs) for the title reaction with the initial nonrotating HS in the ground and the (100) and (001) vibrational excited states. It is found that the fundamental symmetric and asymmetric stretching excitations of HS exhibit almost the same influence on the DCS, but unlike the H + HO → H + OH reaction, they greatly increase the vibrational excitation of both the H and SH products. The hot vibrational state distributions of H are consistent with the prediction of product energy disposal by Polanyi's rules for an early barrier reaction. Because the incident H atom reacts strongly with both the ground and excited S-H states, the large populations of product SH( = 1), which are very close to the relative reactivity of the initial S-H( = 0) state, can still be explained by the local mode picture for HS and the nonreacting SH bond's spectator nature.
我们采用含时波包方法，计算了初始处于基态及（100）和（001）振动激发态且不旋转的HS与标题反应的首个全维（6D）态-态微分截面（DCS）。结果发现，HS的基本对称和不对称伸缩激发对DCS的影响几乎相同，但与H + HO → H + OH反应不同的是，它们极大地增加了H和SH产物的振动激发。H的热振动态分布与早期势垒反应的Polanyi规则对产物能量分配的预测一致。由于入射H原子与基态和激发态的S-H态都强烈反应，产物SH（= 1）的大量分布，其与初始S-H（= 0）态的相对反应性非常接近，仍然可以用HS的局域模图像和非反应性SH键的旁观性质来解释。
