Meng Qingyong, Schröder Markus, Meyer Hans-Dieter
Department of Chemistry, Northwestern Polytechnical University, West Youyi Road 127, 710072 Xi'an, China.
Theoretische Chemie, Physikalisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
J Chem Theory Comput. 2021 May 11;17(5):2702-2713. doi: 10.1021/acs.jctc.1c00241. Epub 2021 Apr 27.
In this work, high-dimensional (21D) quantum dynamics calculations on the mode-specific surface scattering of a carbon monoxide molecule on a copper(100) surface with lattice effects of a five-atom surface cell are performed through the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. We employ a surface model in which five surface atoms near the impact site are treated as fully flexible quantum particles, while all other more distant atoms are kept at fixed locations. To efficiently perform the 21D ML-MCTDH wave packet propagation, the potential energy surface is transferred to a canonical polyadic decomposition form with the aid of a Monte Carlo-based method. Excitation-specific sticking probabilities of CO on Cu(100) are computed, and lattice effects caused by the flexible surface atoms are demonstrated by comparison with sticking probabilities computed for a rigid surface. The dependence of the sticking probability of the initial state of the system is studied, and it is found that the sticking probability is reduced when the surface atom on the impact site is initially vibrationally excited.
在这项工作中，通过多层多组态含时 Hartree（ML-MCTDH）方法，对一氧化碳分子在具有五原子表面单元晶格效应的铜（100）表面上的模式特定表面散射进行了高维（21 维）量子动力学计算。我们采用一种表面模型，其中将撞击位点附近的五个表面原子视为完全灵活的量子粒子，而所有其他更远的原子保持在固定位置。为了有效地进行 21 维 ML-MCTDH 波包传播，借助基于蒙特卡罗的方法将势能面转换为规范多原子分解形式。计算了 CO 在 Cu(100)上特定激发的吸附概率，并通过与刚性表面计算的吸附概率进行比较，展示了由灵活表面原子引起的晶格效应。研究了系统初始状态的吸附概率的依赖性，发现当撞击位点上的表面原子最初处于振动激发态时，吸附概率会降低。
