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

MPS-Authors
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Geweke,  J.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

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Shirhatti,  P. R.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

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Bartels,  C.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

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Wodtke,  A. M.
Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society;

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Fulltext (public)

2335556.pdf
(Publisher version), 3MB

Supplementary Material (public)

2335556_Suppl.docx
(Supplementary material), 742KB

Citation

Geweke, J., Shirhatti, P. R., Rahinov, I., Bartels, C., & Wodtke, A. M. (2016). Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111). Journal of Chemical Physics, 145: 054709. doi:10.1063/1.4959968.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002B-346D-F
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.