title: Mode specificity for the dissociative chemisorption of H2O on Cu(111): a quantum dynamics study on an accurately fitted potential energy surface.
abstract: The mode-specific dynamics for the dissociative chemisorption of H2O on Cu(111) is first investigated by seven-dimensional quantum dynamics calculations, based on an accurately fitted potential energy surface (PES) recently developed by neural network fitting to DFT energy points. It is indicated that excitations in all three vibrational modes have a significant impact on reactivity, which are more efficacious than increasing the translational energy in promoting the reaction, with the largest enhancement for the excitation in the asymmetric stretching mode. There is large discrepancy between the six-dimensional reactivities with fixed azimuthal angles and seven-dimensional results, revealing that the 6D "flat surface" model cannot accurately characterize the reaction dynamics. The azimuthal angle-averaging approach is validated for vibrational excited states of the reactant, where the 7D mode-specific probability can be well reproduced by averaging the 6D azimuthal angle-fixed probabilities over 18 angles.
authors.affiliation: 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, P. R. China. bina@dicp.ac.cn zhangdh@dicp.ac.cn and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China.
authors.forename: Tianhui
authors.initials: T
authors.lastname: Liu
authors.affiliation: 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, P. R. China. bina@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Zhaojun
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: 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, P. R. China. bina@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Bina
authors.initials: B
authors.lastname: Fu
authors.affiliation: 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, P. R. China. bina@dicp.ac.cn zhangdh@dicp.ac.cn and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China.
authors.forename: Xueming
authors.initials: X
authors.lastname: Yang
authors.affiliation: 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, P. R. China. bina@dicp.ac.cn zhangdh@dicp.ac.cn.
authors.forename: Dong H
authors.initials: DH
authors.lastname: Zhang