Liu Tianhui, Fu Bina, Zhang Dong H
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. 2014 Apr 14;140(14):144701. doi: 10.1063/1.4870594.
We carried out six-dimensional quantum dynamics calculations for the dissociative adsorption of deuterium chloride (DCl) on Au(111) surface using the initial state-selected time-dependent wave packet approach. The four-dimensional dissociation probabilities are also obtained with the center of mass of DCl fixed at various sites. These calculations were all performed based on an accurate potential energy surface recently constructed by neural network fitting to density function theory energy points. The origin of the extremely small dissociation probability for DCl/HCl (v = 0, j = 0) fixed at the top site compared to other fixed sites is elucidated in this study. The influence of vibrational excitation and rotational orientation of DCl on the reactivity was investigated by calculating six-dimensional dissociation probabilities. The vibrational excitation of DCl enhances the reactivity substantially and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. The site-averaged dissociation probability over 25 fixed sites obtained from four-dimensional quantum dynamics calculations can accurately reproduce the six-dimensional dissociation probability.
我们使用初始态选择的含时波包方法，对氯化氘（DCl）在Au(111)表面的解离吸附进行了六维量子动力学计算。通过将DCl的质心固定在不同位置，还得到了四维解离概率。这些计算均基于最近通过神经网络拟合密度泛函理论能量点构建的精确势能面进行。本研究阐明了与其他固定位置相比，固定在顶位的DCl/HCl（v = 0，j = 0）解离概率极小的原因。通过计算六维解离概率，研究了DCl的振动激发和转动取向对反应活性的影响。DCl的振动激发显著增强了反应活性，并且直升机取向比车轮取向产生更高的解离概率。从四维量子动力学计算得到的25个固定位置上的位点平均解离概率能够准确再现六维解离概率。
