The electron-induced reaction of physisorbed vinyl bromide (ViBr) and allyl bromide (AllBr) on Cu(110) at 4.6 K was studied experimentally by scanning tunneling microscopy and theoretically by molecular dynamics. ViBr and AllBr were found to react by two pathways: “Direct”, in which the molecule reacted under the tip, and “Delayed”, in which reaction occurred spontaneously after the molecule had diffused across the surface away from the tip. The novel pathway of Delayed reaction constituted a major route for both vinyl bromide (68%) and allyl bromide (53%). The observed reaction dynamics for ViBr and AllBr gave evidence of a long-lived vibrationally excited intermediate for both Direct and Delayed reactions. Molecular dynamics simulations with reagent excitation by way of selected vibrational normal modes resulted in either Direct or Delayed reaction, depending on the vibrational mode.

中文翻译：

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电子诱导的表面反应的直接和延迟动力学

通过扫描隧道显微镜和理论上的分子动力学实验研究了物理吸附的乙烯基溴（ViBr）和烯丙基溴（AllBr）在4.6 K时在Cu（110）上的电子诱导反应。发现ViBr和AllBr通过两种途径发生反应：“直接”（Direct）和“延迟”（Delayed），分子在尖端下方反应，该分子在尖端下方发生反应，而“延迟”（Delayed）在分子从尖端向外扩散到整个表面后自发发生。延迟反应的新途径是乙烯基溴（68％）和烯丙基溴（53％）的主要途径。观察到的ViBr和AllBr的反应动力学为直接反应和延迟反应提供了长寿命的振动激发中间体。