On-the-Fly Symmetrical Quasi-Classical Dynamics with Meyer-Miller Mapping Hamiltonian for the Treatment of Nonadiabatic Dynamics at Conical Intersections.

Abstract

The on-the-fly version of the symmetrical quasi-classical dynamics method based on the Meyer-Miller mapping Hamiltonian (SQC/MM) is implemented to study the nonadiabatic dynamics at conical intersections of polyatomic systems. The current on-the-fly implementation of the SQC/MM method is based on the adiabatic representation and the dressed momentum. To include the zero-point energy (ZPE) correction of the electronic mapping variables, we employ both the γ-adjusted and γ-fixed approaches. Nonadiabatic dynamics of the methaniminium cation (CH2NH2+) and azomethane are simulated using the on-the-fly SQC/MM method. For CH2NH2+, both ZPE correction approaches give reasonable and consistent results. However, for azomethane, the γ-adjusted version of the SQC/MM dynamics behaves much better than the γ-fixed version. Further analysis indicates that it is always recommended to use the γ-adjusted SQC/MM dynamics in the on-the-fly simulation of photoinduced dynamics of polyatomic systems, particularly when the excited state is well separated from the ground state in the Franck-Condon region. This work indicates that the on-the-fly SQC/MM method is a powerful simulation protocol to deal with the nonadiabatic dynamics of realistic polyatomic systems.