Liu Tianhui, Fu Bina, Zhang Dong H
State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P. R. China.
Phys Chem Chem Phys. 2017 May 17;19(19):11960-11967. doi: 10.1039/c7cp01770g.
The mode specificity of the dissociative chemisorption of DO on a rigid Cu(111) surface was investigated by calculating the approximate full-dimensional (9D) dissociation probabilities with the implementation of the seven-dimensional (7D) quantum dynamics calculations and site averaging approximations. The approximate 9D dissociation probabilities for DO initially in various vibrational states were obtained by averaging the site-specific 7D results over 9 impact sites on an accurate 9D potential energy surface (PES). Strong mode specificity was observed for the title reaction, where vibrational excitations of the two stretching modes of DO are more efficacious than increasing the translational energy in promoting the reaction, while the bending excitations with one and two quanta are less efficacious than the same amount of translational energy in enhancing the reactivity at low kinetic energies.
通过实施七维（7D）量子动力学计算和位点平均近似来计算近似全维（9D）解离概率，研究了DO在刚性Cu(111)表面上的解离化学吸附的模式特异性。通过在精确的9D势能面（PES）上的9个碰撞位点对位点特异性的7D结果进行平均，获得了初始处于各种振动状态的DO的近似9D解离概率。对于该标题反应观察到了强烈的模式特异性，其中DO的两个伸缩模式的振动激发在促进反应方面比增加平动能更有效，而具有一个和两个量子的弯曲激发在低动能下增强反应性方面比相同量的平动能效果更差。
