Nonadiabatic Dynamics near Metal Surfaces with Periodic Drivings: A Generalized Surface Hopping in Floquet Representation.

With light-matter interaction extending into the strong regime, as well as rapid development of laser technology, systems subjecting to a time-periodic perturbation have attracted broad attention. Floquet theorem and Floquet time-independent Hamiltonian are powerful theoretical frameworks to investigate the systems subjected to time-periodic drivings. In this study, we extend the previous generalized surface hopping (SH) algorithm near a metal surface (J. Chem. Theory Comput. 2017, 13, 6, 2430-2439) to the Floquet space, and hence, we develop a generalized Floquet representation-based SH (FR-SH) algorithm. Here, we consider an open quantum system with fast drivings. We expect that the present algorithm will be useful for understanding the chemical processes of molecules under time-periodic driving near the metal surface.