Song Qingfei, Zhang Xingyu, Gatti Fabien, Miao Zekai, Zhang Qiuyu, Meng Qingyong
Department of Chemistry, Northwestern Polytechnical University, West Youyi Road 127, 710072 Xi'an, China.
Institut des Sciences Moléculaires d'Orsay, CNRS-UMR 8214, Université Paris-Saclay, Bâtiment 520, F-91405 Orsay, France.
J Phys Chem A. 2022 Sep 15;126(36):6047-6058. doi: 10.1021/acs.jpca.2c03092. Epub 2022 Sep 2.
In this work, full-dimensional (9D) quantum dynamics calculations on mode-/bond-specific surface scattering of a water molecule on a copper (111) rigid surface are performed through the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. To easily perform the ML-MCTDH calculations on such a triatomic molecule-surface system, we first choose specific Jacobi coordinates as a set of coordinates of water. Next, to efficiently perform the 9D ML-MCTDH wavepacket propagation, the potential energy surface is transferred to a canonical polyadic decomposition form with the aid of a Monte Carlo-based method. Excitation-specific dissociation probabilities of HO on Cu(111) are computed, and mode-/bond-specific dynamics are demonstrated by comparison with a probability curve computed for a water molecule in the ground state. The dependence of the dissociation probability of the initial state of HO is studied, and it is found that the excitation-specific dissociation probabilities can be divided into three groups. We find that the vibrationally excited states enhance the dissociation reactivity of HO, while the rotationally excited states hardly influence it.
在这项工作中，通过多层多组态含时 Hartree（ML-MCTDH）方法对水分子在铜（111）刚性表面上的模式/键特异性表面散射进行了全维（9D）量子动力学计算。为了便于在此三原子分子-表面系统上进行 ML-MCTDH 计算，我们首先选择特定的雅可比坐标作为水的一组坐标。接下来，为了有效地进行 9D ML-MCTDH 波包传播，借助基于蒙特卡罗的方法将势能面转换为正则多原子分解形式。计算了 HO 在 Cu(111)上的特定激发解离概率，并通过与基态水分子计算得到的概率曲线进行比较，展示了模式/键特异性动力学。研究了 HO 初始态解离概率的依赖性，发现特定激发解离概率可分为三组。我们发现振动激发态增强了 HO 的解离反应活性，而转动激发态几乎对其没有影响。
