State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
Nat Commun. 2016 Jun 10;7:11953. doi: 10.1038/ncomms11953.
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.
尽管在过去几十年中取得了重大进展，但在全维量子力学水平上研究分子物种在表面上的离解化学吸附动力学仍然极具挑战性，特别是对于多原子表面反应。在这里，我们报告了迄今为止首次对刚性 Cu(111)上 H2O 的离解化学吸附进行的全维量子动力学研究，其中所有九个分子自由度都完全耦合，基于精确的全维势能面。全维量子力学反应性提供了最高精度的动力学特征，表明 H2O 振动模式的激发比增加平移能更有效地促进反应。不对称伸缩的激发增强最大，但在非常低的能量下，对称伸缩的激发变得可比。全维特征还允许研究以前的降维和近似动力学模型的有效性。
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