First-Principles Insights into Adiabatic and Nonadiabatic Vibrational Energy-Transfer Dynamics during Molecular Scattering from Metal Surfaces: The Importance of Surface Reactivity.

Abstract

Energy transfer is ubiquitous during molecular collisions and reactions at gas-surface interfaces. Of particular importance is vibrational energy transfer because of its relevance to bond forming and breaking. In this Perspective, we review recent first-principles studies on vibrational energy-transfer dynamics during molecular scattering from metal surfaces at the state-to-state level. Taking several representative systems as examples, we highlight the intrinsic correlation between vibrational energy transfer in nonreactive scattering and surface reactivity and how it operates in both electronically adiabatic and nonadiabatic pathways. Adiabatically, the presence of a dissociation barrier softens a bond in the impinging molecule and increases its couplings with other molecular modes and surface phonons. In the meantime, the stronger interaction between the molecule and the surface also changes the electronic structure at the barrier, resulting in an increase of nonadiabatic effects. We further discuss future prospects toward a more quantitative understanding of this important surface dynamical process.