Initial Sampling in Symmetrical Quasiclassical Dynamics Based on Li-Miller Mapping Hamiltonian

Abstract: A symmetrical quasiclassical (SQC) dynamics approach based on the Li-Miller (LM) mapping Hamiltonian (SQC-LM) was employed to describe nonadiabatic dynamics. In principle, the different initial sampling procedures may be applied in the SQC-LM dynamics, and the results may be dependent on the initial sampling. We provided various initial sampling approaches and checked their influence. We selected two groups of models including site-exciton models for exciton dynamics and linear vibronic coupling models for conical intersections to test the performance of SQC-LM dynamics with the different initial sampling methods. The results were examined with respect to those of the accurate multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) quantum dynamics. For both two models, the SQC-LM method more-or-less gives a reasonable description of the population dynamics, while the influence of the initial sampling approaches on the final results is noticeable. It seems that the proper initial sampling methods should be determined by the system under study. This indicates that the combination of the SQC-LM method with a suitable sampling approach may be a potential method in the description of nonadiabatic dynamics.