Negative Zero-Point-Energy Parameter in the Meyer–Miller Mapping Model for Nonadiabatic Dynamics

The celebrated Meyer-Miller mapping model has been a useful approach for generating practical trajectory-based nonadiabatic dynamics methods. It is generally assumed that the zero-point-energy (ZPE) parameter positive. constraint implied in conventional Hamiltonian an F-electronic-state system actually requires \gamma larger than -1/F ZPE each electronic degree of freedom. Both negative and positive values are possible such parameter. We first establish rigorous formulation to construct exact models Cartesian phase space when applied. When nuclear approximated by linearized semiclassical initial value representation, could lead reasonably good performance describing dynamic behaviors typical spin-boson condensed-phase two-state systems, even at challenging zero temperature.