Dynamics in reactions on metal surfaces: A theoretical perspective

Recent advances in theoretical characterization of reaction dynamics on metal surfaces are reviewed. It is shown that the widely available density functional theory of metals and their interactions with molecules have enabled first principles theoretical models for treating surface reaction dynamics. The new theoretical tools include methods to construct high-dimensional adiabatic potential energy surfaces, to characterize nonadiabatic processes within the electronic friction models, and to describe dynamics both quantum mechanically and classically. Three prototypical surface reactions, namely, dissociative chemisorption, Eley-Rideal reactions, and recombinative desorption, are surveyed with a focus on some representative examples. While principles governing gas phase reaction dynamics may still be applicable, the presence of the surface introduces a higher level of complexity due to strong interaction between the molecular species and metal substrate. Furthermore, most of these reactive processes are impacted by energy exchange with surface phonons and/or electron-hole pair excitations. These theoretical studies help to interpret and rationalize experimental observations and, in some cases, guide experimental explorations. Knowledge acquired in these fundamental studies is expected to impact many practical problems in a wide range of interfacial processes.