Shen Xiangjian, Zhang Zhaojun, Zhang Dong H
Research Center of Heterogeneous Catalysis and Engineering Sciences, School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China.
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. 2016 Mar 14;144(10):101101. doi: 10.1063/1.4943128.
Understanding the role of reactant ro-vibrational degrees of freedom (DOFs) in reaction dynamics of polyatomic molecular dissociation on metal surfaces is of great importance to explore the complex chemical reaction mechanism. Here, we present an expensive quantum dynamics study of the dissociative chemisorption of CH4 on a rigid Ni(111) surface by developing an accurate nine-dimensional quantum dynamical model including the DOF of azimuth. Based on a highly accurate fifteen-dimensional potential energy surface built from first principles, our simulations elucidate that the dissociation probability of CH4 has the strong dependence on azimuth and surface impact site. Some improvements are suggested to obtain the accurate dissociation probability from quantum dynamics simulations.
了解反应物的转动 - 振动自由度（DOFs）在多原子分子在金属表面解离反应动力学中的作用，对于探索复杂的化学反应机理至关重要。在此，我们通过建立一个精确的包含方位角自由度的九维量子动力学模型，对CH4在刚性Ni(111)表面的解离化学吸附进行了一项计算量较大的量子动力学研究。基于从第一性原理构建的高精度十五维势能面，我们的模拟结果表明，CH4的解离概率强烈依赖于方位角和表面碰撞位点。为了从量子动力学模拟中获得准确的解离概率，我们提出了一些改进建议。
