State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
J Chem Phys. 2013 Nov 14;139(18):184705. doi: 10.1063/1.4829508.
The six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on Au(111) are carried out using the time-dependent wave-packet approach, based on an accurate PES which was recently developed by neural network fitting to density functional theory energy points. The influence of vibrational excitation and rotational orientation of HCl on the reactivity is investigated by calculating the exact six-dimensional dissociation probabilities, as well as the four-dimensional fixed-site dissociation probabilities. The vibrational excitation of HCl enhances the reactivity and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. A new interesting site-averaged effect is found for the title molecule-surface system that one can essentially reproduce the six-dimensional dissociation probability by averaging the four-dimensional dissociation probabilities over 25 fixed sites.
采用基于时间的波包方法，基于最近通过神经网络拟合密度泛函理论能量点而开发的精确 PES，对 HCl 在 Au(111)上的离解化学吸附的六维量子动力学进行了计算。通过计算精确的六维离解概率以及四维固定位离解概率，研究了 HCl 的振动激发和旋转取向对反应性的影响。HCl 的振动激发增强了反应性，直升机取向比车轮取向产生更高的离解概率。对于标题分子-表面体系，发现了一个新的有趣的平均站点效应，即通过在 25 个固定位上平均四维离解概率，可以基本上再现六维离解概率。
