Coherence-Controlled Nonadiabatic Dynamics via State-Space Decomposition: A Consistent Way To Incorporate Ehrenfest and Born-Oppenheimer-Like Treatments of Nuclear Motion.

Accurately describing nuclear motion is crucial in electronically nonadiabatic dynamics simulations. In this work, a coherence-controlled (CC) approach is proposed based on the mapping between the classical state space and the full electronic matrix and that between the decomposed state space and different nuclear dynamics that allows nuclear motion to properly follow either Ehrenfest dynamics in the coherence domain or Born-Oppenheimer-like dynamics in the single-state domain in a consistent manner. This new method is applied to several benchmark models involving nonadiabatic transitions in two-state or three-state systems, and the obtained results are in excellent agreement with exact quantum calculations. As a generalization of the recently developed symmetrical quasiclassical approach and the augmented image (AI) version of the multistate trajectory approach, the proposed method is extremely efficient and numerically stable. Therefore, it has great potential for implementation in nonadiabatic molecular dynamics simulations for realistic complex systems, such as materials and biological molecules.