Dutta Joy, Mandal Souvik, Adhikari Satrajit, Spiering Paul, Meyer Jörg, Somers Mark F
School of Chemical Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India.
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
J Chem Phys. 2021 Mar 14;154(10):104103. doi: 10.1063/5.0035830.
The effect of surface atom vibrations on H scattering from a Cu(111) surface at different temperatures is being investigated for hydrogen molecules in their rovibrational ground state (v = 0, j = 0). We assume weakly correlated interactions between molecular degrees of freedom and surface modes through a Hartree product type wavefunction. While constructing the six-dimensional effective Hamiltonian, we employ (a) a chemically accurate potential energy surface according to the static corrugation model [M. Wijzenbroek and M. F. Somers, J. Chem. Phys. 137, 054703 (2012)]; (b) normal mode frequencies and displacement vectors calculated with different surface atom interaction potentials within a cluster approximation; and (c) initial state distributions for the vibrational modes according to Bose-Einstein probability factors. We carry out 6D quantum dynamics with the so-constructed effective Hamiltonian and analyze sticking and state-to-state scattering probabilities. The surface atom vibrations affect the chemisorption dynamics. The results show physically meaningful trends for both reaction and scattering probabilities compared to experimental and other theoretical results.
对于处于振转基态（v = 0，j = 0）的氢分子，正在研究不同温度下表面原子振动对从Cu(111)表面散射H的影响。我们通过Hartree积型波函数假设分子自由度与表面模式之间存在弱关联相互作用。在构建六维有效哈密顿量时，我们采用：(a) 根据静态起伏模型[M. Wijzenbroek和M. F. Somers，《化学物理杂志》137, 054703 (2012)]得到的化学精确势能面；(b) 在簇近似内用不同表面原子相互作用势计算得到的简正模式频率和位移矢量；以及(c) 根据玻色 - 爱因斯坦概率因子得到的振动模式的初始态分布。我们用如此构建的有效哈密顿量进行六维量子动力学计算，并分析吸附和态 - 态散射概率。表面原子振动影响化学吸附动力学。与实验结果和其他理论结果相比，结果显示出反应概率和散射概率具有物理意义的趋势。
