Direct and Delayed Dynamics in Electron-Induced Surface Reaction

Oliver MacLean, Kai Huang, Lydie Leung, John C. Polanyi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations


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.

Original languageEnglish
Pages (from-to)17368-17375
Number of pages8
JournalJournal of the American Chemical Society
Issue number48
StatePublished - 6 Dec 2017
Externally publishedYes


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