Issue 21, 2024

Vibrational energy transfer in collisions of molecules with metal surfaces

Abstract

The Born–Oppenheimer approximation (BOA), which serves as the basis for our understanding of chemical bonding, reactivity and dynamics, is routinely violated for vibrationally inelastic scattering of molecules at metal surfaces. The title-field therefore represents a fascinating challenge to our conventional wisdom calling for new concepts that involve explicit electron dynamics occurring in concert with nuclear motion. Here, we review progress made in this field over the last decade, which has witnessed dramatic advances in experimental methods, thereby providing a much more extensive set of diverse observations than has ever before been available. We first review the experimental methods used in this field and then provide a systematic tour of the vast array of observations that are currently available. We show how these observations – taken together and without reference to computational simulations – lead us to a simple and intuitive picture of BOA failure in molecular dynamics at metal surfaces, one where electron transfer between the molecule and the metal plays a preeminent role. We also review recent progress made in the theory of electron transfer mediated BOA failure in molecule–surface interactions, describing the most important methods and their ability to reproduce experimental observation. Finally, we outline future directions for research and important unanswered questions.

Graphical abstract: Vibrational energy transfer in collisions of molecules with metal surfaces

Article information

Article type
Perspective
Submitted
04 3 2024
Accepted
27 4 2024
First published
29 4 2024
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024,26, 15090-15114

Vibrational energy transfer in collisions of molecules with metal surfaces

I. Rahinov, A. Kandratsenka, T. Schäfer, P. Shirhatti, K. Golibrzuch and A. M. Wodtke, Phys. Chem. Chem. Phys., 2024, 26, 15090 DOI: 10.1039/D4CP00957F

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