Mode specificity of the dissociative chemisorption of HOD on rigid Cu(111): an approximate full-dimensional quantum dynamics study
Mode specificity of the dissociative chemisorption of HOD on rigid Cu(111): an approximate full-dimensional quantum dynamics study
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HOD 在刚性 Cu(111) 上解离化学吸附的模式特异性：近似全维量子动力学研究
DOI：
10.1039/c6cp04690h
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发表时间：
2016
影响因子：
3.3
通讯作者：
Zhang Dong H.
中科院分区：
文献类型：
--
作者：
Liu Tianhui;Zhang Zhaojun;Chen Jun;Fu Bina;Zhang Dong H.
在最近的H_2O/Cu（111）体系的研究中，我们证实了精确势位平均近似（SAEP）的有效性[Z. Zhang，T.刘，B。Fu，X. Yang，杨氏D. H.张，国家通讯社2016，7，11953]。本文通过在精确的九维（9D）势能面上进行七维（7 D）量子动力学计算和SAEP的实现，研究了HOD在刚性Cu（111）表面解离化学吸附的模式特异性.通过对9个撞击点的7 D结果进行平均，得到了初始处于不同振动态的HOD的近似9D离解概率。一个强大的键选择性效应的标题反应观察到，一个特定的键的振动激发导致一个大的增强，只有在反应中，激发键被打破。产物分支比强烈地依赖于哪个键被激发，并且来自激发键的断裂的产物比其他产物更有利。SAEP的实现使我们能够在只有在全维量子动力学计算中才能实现的精度水平上研究特定模式的动力学。
The validity of the site averaging approximation with exact potential (SAEP) has been confirmed in a recent work on the H2O/Cu(111) system [Z. Zhang, T. Liu, B. Fu, X. Yang, D. H. Zhang, Nat. Commun. 2016, 7, 11953]. Here, the mode specificity of the dissociative chemisorption of HOD on a rigid Cu(111) surface is investigated by carrying out the seven-dimensional (7D) quantum dynamics calculations on an accurate nine-dimensional (9D) potential energy surface together with the implementation of the SAEP. The approximate 9D dissociation probabilities for HOD initially in various vibrational states are obtained by averaging the site-specific 7D results over 9 impact sites. A strong bond-selective effect for the title reaction is observed, where vibrational excitation of a particular bond leads to a large enhancement only in the reaction in which the excited bond is broken. The product branching ratios strongly depend on which bond is excited, and the product from the cleavage of the excited bond is much more favored than the other product. The implementation of the SAEP allows us to investigate the mode-specific dynamics at a level of accuracy that can only be achieved in full-dimensional quantum dynamics calculations.