A reciprocal-space formulation of surface hopping.

Abstract

Surface hopping has seen great success in describing molecular phenomena where electronic excitations tend to be localized, but its application to materials with band-like electronic properties has remained limited. Here, we derive a formulation of fewest-switches surface hopping where both the quantum and classical equations of motion are solved entirely in terms of reciprocal-space coordinates. The resulting method is directly compatible with band structure calculations and allows for the efficient description of band-like phenomena by means of a truncation of the Brillouin zone. Using the Holstein and Peierls models as examples, we demonstrate the formal equivalence between real-space and reciprocal-space surface hopping and assess their accuracy against mean-field mixed quantum-classical dynamics and numerically exact results. Having very similar equations of motion, reciprocal-space surface hopping can be straightforwardly incorporated in existing (real-space) surface hopping implementations.