Departamento de Química Física, Universidad de Salamanca, 37008 Salamanca, Spain.
J Phys Chem A. 2009 Dec 31;113(52):14237-50. doi: 10.1021/jp902336s.
The dynamics of the O((1)D) + HCl(v = 0, j = 0) --> Cl + OH reaction at a 0.26 eV collision energy has been investigated by means of a quasiclassical trajectory (QCT) and statistical quantum and quasiclassical methods. State-resolved cross sections and Cl atom velocity distributions have been calculated on two different potential energy surfaces (PESs): the H2 surface (Martinez et al. Phys. Chem. Chem. Phys. 2000, 2, 589) and the latest surface by Peterson, Bowman, and co-workers (PSB2) (J. Chem. Phys. 2000, 113, 6186). The comparison with recent experimental results reveals that the PSB2 PES manages to describe correctly differential cross sections and the velocity distributions of the departing Cl atom. The calculations on the H2 PES seem to overestimate the OH scattering in the forward direction and the fraction of Cl at high recoil velocities. Although the comparison of the corresponding angular distributions is not bad, significant deviations with a statistical description are found, thus ruling out a complex-forming mechanism as the dominant reaction pathway. However, for the ClO + H product channel, the QCT and statistical predictions are found to be in good agreement.
在 0.26eV 碰撞能下，通过准经典轨迹（QCT）和统计量子和准经典方法研究了 O((1)D) + HCl(v = 0, j = 0) --> Cl + OH 反应的动力学。在两个不同的势能面上（PESs）计算了态分辨截面和 Cl 原子速度分布：H2 表面（Martinez 等人，Phys. Chem. Chem. Phys. 2000, 2, 589）和 Peterson、Bowman 及其同事的最新表面 PSB2（J. Chem. Phys. 2000, 113, 6186）。与最近的实验结果的比较表明，PSB2 PES 成功地描述了微分截面和离去 Cl 原子的速度分布。在 H2 PES 上的计算似乎高估了 OH 在向前方向的散射和高反冲速度下 Cl 的分数。尽管对应的角分布比较不差，但发现与统计描述有显著偏差，从而排除了形成复合物的机制作为主要反应途径。然而，对于 ClO + H 产物通道，QCT 和统计预测被发现是一致的。
