Electronic energy dissipation during scattering of vibrationally excited molecules at metal surfaces: ab initio simulations for HCl/Al(111).
Electronic energy dissipation during scattering of vibrationally excited molecules at metal surfaces: ab initio simulations for HCl/Al(111).
复制标题
金属表面振动激发分子散射过程中的电子能量耗散：HCl/Al(111) 的从头算模拟。
DOI：
10.1103/physrevlett.112.043201
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发表时间：
2014
影响因子：
8.6
通讯作者：
E. Pehlke
中科院分区：
文献类型：
--
作者：
Michael Grotemeyer;E. Pehlke
在这封信中，报道了基于电子的时间相关密度泛函理论和原子核的 Ehrenfest 动力学的从头算分子动力学模拟，详细描述了振动 HCl 分子与 Al(111) 基质的相互作用。在高度振动激发的分子的情况下，负责强电子空穴对 (EHP) 振动耦合的机制可追溯到 spz* 类反键 HCl 最低未占据分子轨道随键长的大本征能位移。由于这种机制，电子激发光谱变得高度不对称。模拟结果解释了如何协调强 EHP 振动耦合（在高度振动激发的分子的情况下）与 Ran 等人在热金表面散射 HCl 分子期间实验观察到的小但明显明显的电子对 v=0 → v=1 振动激发的贡献。 [物理。莱特牧师。 98 237601（2007）]。
In this Letter, ab initio molecular dynamics simulations based on time-dependent density functional theory for the electrons and Ehrenfest dynamics for the nuclei are reported that detail the interaction of a vibrating HCl molecule with an Al(111) substrate. The mechanism responsible for the strong electron-hole-pair (EHP)-vibrational coupling in case of highly vibrationally excited molecules is traced back to a large eigenenergy shift of the spz*-like antibonding HCl lowest unoccupied molecular orbital with the bond length. As a consequence of this mechanism, the electronic excitation spectra turn out to be highly asymmetric. The simulations suggest an explanation of how to reconcile a strong EHP-vibrational coupling in case of highly vibrationally excited molecules with the small, but clearly evident, electronic contribution to the v=0 → v=1 vibrational excitation observed experimentally during the scattering of HCl molecules at a hot Au surface by Ran et al. [Phys. Rev. Lett. 98 237601 (2007)].