Energy transfer and chemical dynamics at solid surfaces: The special role of charge transfer

Molecular energy transfer processes at solid surfaces are profoundly important, influencing trapping, desorption, diffusion, and reactivity; in short, all of the elementary steps needed for surface chemistry to take place. In this paper we review recent progress in our understanding of energy transfer at surfaces with a particular emphasis on those phenomena, which are peculiar to solids with delocalized electronic structure, e.g. electronically nonadiabatic energy transfer. This area of study represents an area requiring significant extensions of our theoretical understanding, which is largely based on density functional theory. This review provides an overview of some of the experimental and theoretical tools presently being used in this field and a description of several illustrative examples of work that have helped to shape our understanding.