Liu Tianhui, Fu Bina, Zhang Dong H
School of Sciences, Great Bay University, Dongguan 523000, China.
Great Bay Institute for Advanced Study, Dongguan 523000, China.
J Chem Phys. 2024 May 7;160(17). doi: 10.1063/5.0201925.
We present a comprehensive investigation into the dissociative chemisorption of HOD on a rigid Ni(100) surface using an approximate full-dimensional (9D) quantum dynamics approach, which was based on the time-dependent wave-packet calculations on a full-dimensional potential energy surface obtained through neural network fitting to density functional theory energy points. The approximate-9D probabilities were computed by averaging the seven-dimensional (7D) site-specific dissociation probabilities across six impact sites with appropriate relative weights. Our results uncover a distinctive bond-selective effect, demonstrating that the vibrational excitation of a specific bond substantially enhances the cleavage of that excited bond. The product branching ratios are substantially influenced by which bond undergoes excitation, exhibiting a clear preference for the product formed through the cleavage of the excited bond over the alternative product.
我们使用一种近似全维（9D）量子动力学方法，对HOD在刚性Ni(100)表面的解离化学吸附进行了全面研究。该方法基于在通过神经网络拟合密度泛函理论能量点获得的全维势能面上进行的含时波包计算。近似9D概率是通过对六个碰撞位点上具有适当相对权重的七维（7D）位点特异性解离概率进行平均来计算的。我们的结果揭示了一种独特的键选择性效应，表明特定键的振动激发显著增强了该激发键的断裂。产物分支比受到激发键的显著影响，与替代产物相比，通过激发键断裂形成的产物表现出明显的偏好。
