Zhang Xu Qiang, Cui Qian, Zhang John Z H, Han Ke Li
Department of Chemistry, New York University, New York, New York 10003, USA.
J Chem Phys. 2007 Jun 21;126(23):234304. doi: 10.1063/1.2745796.
We report in this paper a quantum dynamics study for the reaction H+NH3-->NH2+H2 on the potential energy surface of Corchado and Espinosa-Garcia [J. Chem. Phys. 106, 4013 (1997)]. The quantum dynamics calculation employs the semirigid vibrating rotor target model [J. Z. H. Zhang, J. Chem. Phys. 111, 3929 (1999)] and time-dependent wave packet method to propagate the wave function. Initial state-specific reaction probabilities are obtained, and an energy correction scheme is employed to account for zero point energy changes for the neglected degrees of freedom in the dynamics treatment. Tunneling effect is observed in the energy dependency of reaction probability, similar to those found in H+CH4 reaction. The influence of rovibrational excitation on reaction probability and stereodynamical effect are investigated. Reaction rate constants from the initial ground state are calculated and are compared to those from the transition state theory and experimental measurement.
我们在本文中报告了一项关于H + NH₃→NH₂ + H₂反应在Corchado和Espinosa - Garcia势能面上的量子动力学研究[《化学物理杂志》106, 4013 (1997)]。量子动力学计算采用半刚性振动转子靶模型[张泽华，《化学物理杂志》111, 3929 (1999)]和含时波包方法来传播波函数。获得了特定初始态的反应概率，并采用能量校正方案来考虑动力学处理中被忽略自由度的零点能变化。在反应概率的能量依赖性中观察到了隧穿效应，这与在H + CH₄反应中发现的情况类似。研究了振转激发对反应概率和立体动力学效应的影响。计算了初始基态的反应速率常数，并与过渡态理论和实验测量得到的结果进行了比较。
