Nonadiabatic Molecular Dynamics at Metal Surfaces.

Dynamics at molecule-metal interfaces are a subject of intense current interest and come in many different flavors of experiments: gas-phase scattering, chemisorption, electrochemistry, nanojunction transport, and heterogeneous catalysis, to name a few. These dynamics involve nuclear degrees of freedom entangled with many electronic degrees of freedom (in the metal), and as such there is always the possibility for nonadiabatic phenomena to appear: the nuclei do not necessarily need to move slower than the electrons to break the Born-Oppenheimer (BO) approximation. In this Feature Article, we review a set of dynamical methods developed recently to deal with such nonadiabatic phenomena at a metal surface, methods that serve as alternatives to Tully's independent electron surface hopping (IESH) model. In the weak molecule-metal coupling regime, a classical master equation (CME) can be derived and a simple surface hopping approach is proposed to propagate nuclear and electronic dynamics stochastically. In the strong molecule-metal interaction regime, a Fokker-Planck equation can be derived for the nuclear dynamics, with electronic DoFs incorporated into the overall friction and random force. Lastly, a broadened classical master equation (BCME) can interpolate between the weak and strong molecule-metal interactions. Here, we briefly review these methods and the relevant benchmarking data, showing in particular how the methods can be used to calculate nonequilibrium transport properties. We highlight several open questions and pose several avenues for future study.