A Generalized Surface Hopping Algorithm to Model Nonadiabatic Dynamics near Metal Surfaces: The Case of Multiple Electronic Orbitals

For a molecule with multiple electronic orbitals and many nuclear degrees of freedom near a metal surface, there is a natural embedding of the quantum-classical Liouville equation inside a classical master equation (QCLE-CME) to model nonadiabatic dynamics (J. Chem. Phys. 2016, 145, 054102). In this paper, we propose a variety of surface hopping algorithms for solving such a QCLE-CME. We find that an augmented surface hopping (A-SH) algorithm works well for propagating such nonadiabatic dynamics (near a metal surface). We expect the present algorithm will be very useful for modeling electrochemical problems in the future.