First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111).
First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111).
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H2O 在刚性 Cu(111) 上解离化学吸附的第一性原理量子动力学理论
DOI：
10.1038/ncomms11953
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发表时间：
2016-06-10
影响因子：
16.6
通讯作者：
Zhang DH
中科院分区：
文献类型：
--
作者：
Zhang Z;Liu T;Fu B;Yang X;Zhang DH
尽管在过去的几十年中取得了重大进展，它仍然是极具挑战性的研究解离化学吸附动力学的分子物种在表面上的全维量子力学水平，特别是多原子表面反应。在这里，我们报告，据我们所知，第一个全维量子动力学研究的解离化学吸附的H2O在刚性铜（111）与所有9个分子自由度完全耦合，基于一个准确的全维势能面。全维量子力学反应性提供了最高精度的动力学特征，揭示了H2O振动模式中的激发比增加平移能更有效地促进反应。非对称拉伸的激发增强最大，而对称拉伸的激发增强在很低的能量下变得相当。全维表征还允许研究以前的降维和近似动力学模型的有效性。
Despite significant progress made in the past decades, it remains extremely challenging to investigate the dissociative chemisorption dynamics of molecular species on surfaces at a full-dimensional quantum mechanical level, in particular for polyatomic-surface reactions. Here we report, to the best of our knowledge, the first full-dimensional quantum dynamics study for the dissociative chemisorption of H2O on rigid Cu(111) with all the nine molecular degrees of freedom fully coupled, based on an accurate full-dimensional potential energy surface. The full-dimensional quantum mechanical reactivity provides the dynamics features with the highest accuracy, revealing that the excitations in vibrational modes of H2O are more efficacious than increasing the translational energy in promoting the reaction. The enhancement of the excitation in asymmetric stretch is the largest, but that of symmetric stretch becomes comparable at very low energies. The full-dimensional characterization also allows the investigation of the validity of previous reduced-dimensional and approximate dynamical models.