Nonadiabatic Dynamics of Hydrogen Diffusion on Cu(001): Classical Mapping Model with Multistate Projection Window in Real Space

Diffusion of atomic hydrogen on metallic surfaces is a longstanding research topic of both fundamental and practical interests. However, full understanding of the microscopic mechanisms and development of effective strategy for surface dynamics control at the molecular level remain elusive. In this paper, we propose a new nonadiabatic multistate model for surface diffusion based on a real space decomposition scheme by generalizing the classical mapping theory of Meyer and Miller. The model suggests a general multistate perspective on real-time surface dynamics by mapping it into spatially disjointed windowing functions, which feature the explicit nonadiabatic controllability. Within this framework, the first nonadiabatic molecular dynamics simulation is performed for atomic hydrogen diffusion on the Cu(001) surface, and the nonequilibrium effect of lattice distortion is studied.