State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
J Chem Phys. 2012 Mar 7;136(9):094308. doi: 10.1063/1.3690051.
We present an exact quantum dynamical study and quasi-classical trajectory (QCT) calculations for the exchange and abstraction processes for the H + HS reaction. These calculations were based on a newly constructed high-quality potential energy surface for the lowest triplet state of H(2)S ((3)A"). The ab initio single-point energies were computed using complete active space self-consistent field and multi-reference configuration interaction method with a basis set of aug-cc-pV5Z. The time-dependent wave packet (TDWP) method was used to calculate the total reaction probabilities and integral cross sections over the collision energy (E(col)) range of 0.0-2.0 eV for the reactant HS initially at the ground state and the first vibrationally excited state. It was found that the initial vibrational excitation of HS enhances both abstraction and exchange processes. In addition, a good agreement is found between QCT and TDWP reaction probabilities at the total momentum J = 0 as a function of collision energy for the H + HS (v = 0, j = 0) reaction.
我们对 H + HS 反应的交换和离解过程进行了精确的量子动力学研究和准经典轨迹（QCT）计算。这些计算是基于新构建的 H(2)S（(3)A"）最低三重态的高质量势能面进行的。从头算单点能使用完全活性空间自洽场和多参考组态相互作用方法与 aug-cc-pV5Z 基组进行计算。时间相关波包（TDWP）方法用于计算反应 HS 处于基态和第一振动激发态时，碰撞能（E(col)）范围为 0.0-2.0 eV 的总反应概率和积分截面。结果发现，HS 的初始振动激发增强了离解和交换过程。此外，在总动量 J = 0 时，H + HS（v = 0，j = 0）反应的 QCT 和 TDWP 反应概率与碰撞能的函数关系非常吻合。
