Multilayer Subsystem Surface Hopping Method for Large-Scale Nonadiabatic Dynamics Simulation with Hundreds of Thousands of States.

We present a multilayer subsystem surface hopping (MSSH) method to deal with nonadiabatic dynamics in large-scale systems. A small subsystem instead of the full system is adopted for surface hopping and is updated on-the-fly to achieve a reliable description of important adiabatic states and the wave function evolution. Additional subsystems for molecular dynamics and statistical description are introduced to further improve the simulation reliability. The global flux hopping probabilities with optimal state assignments are utilized to treat the complex surface crossings. As demonstrated in a series of one- and two-dimensional Holstein models with up to hundreds of thousands of states, MSSH shows weak parameter dependence in all investigated systems. Especially, the computational costs are reduced by 2-6 orders of magnitude compared to traditional surface hopping simulations in full systems, and size-independent results are achieved with a large time-step size of 2-5 fs. The new method is compatible with different decoherence correction strategies and achieves a much better balance between efficiency and reliability, thus promising for applications in general charge and exciton dynamics simulations.