Abstract
Here we review experimental and theoretical work on vibrational energy transfer in collisions of molecules with surfaces. We focus on metal surfaces and on the role of non-adiabatic electronic transitions in these collisions. Non-adiabatic electronic transitions contribute to vibrational excitation via the decay of thermally excited electron–hole pairs; conversely, vibrational relaxation can effectively couple vibrational excitation to the production of excited electron–hole pairs. In the case of low work function surfaces, the hot electrons can be observed directly as Vibrationally Promoted Electron Emission (VPPE). The energy distributions of VPEE, and comparison of results on vibrational excitation and relaxation to kinetic models and to ab initio theories all indicate that the non-adiabatic coupling is strong and cannot be properly described by perturbative, weak coupling description. A recently developed model based on ab initio potentials and non-adiabatic couplings and on the Independent Electron Surface Hoping (IESH) model is quite successful in describing both vibrational excitation and relaxation for NO collisions with Au(111) within the same theoretical framework.
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We gratefully acknowledge the Alexander von Humboldt Foundation for support for this work.
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Auerbach, D.J., Wodtke, A.M. (2013). Vibrational Energy Transfer at Surfaces: The Importance of Non-Adiabatic Electronic Effects. In: Díez Muiño, R., Busnengo, H. (eds) Dynamics of Gas-Surface Interactions. Springer Series in Surface Sciences, vol 50. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-32955-5_11
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