Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

Jan Geweke, Pranav R. Shirhatti, Igor Rahinov, Christof Bartels, Alec M. Wodtke

Research output: Contribution to journalArticlepeer-review

30 Scopus citations

Abstract

In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl(v = 0 → 1) and HCl(v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl(v = 2 → 3) channel could not be observed - presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl(v = 0 → 1) excitation probabilities [Q. Ran et al., Phys. Rev. Lett. 98, 237601 (2007)] - 50 times smaller than those reported here - were influenced by erroneous assignment of spectroscopic lines used in the data analysis.

Original languageEnglish
Article number054709
JournalJournal of Chemical Physics
Volume145
Issue number5
DOIs
StatePublished - 7 Aug 2016
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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