Matching-pursuit/split-operator Fourier-transform simulations of nonadiabatic quantum dynamics

摘要

A rigorous and practical approach for simulations of nonadiabatic. quantum dynamics is, introduced. The algorithm involves a natural extension of the matching-pursuit/split-operator Fourier-transform (MP/SOFT) method [Y. Wu and V. S. Batista, J. Chem. Phys. 121, 1676 (2004)] recently developed for simulations of adiabatic quantum dynamics in multidimensional systems. The MP/SOFT propagation scheme, extended to nonadiabatic dynamics, recursively applies the time-evolution operator as defined by the standard perturbation expansion to first-, or second-order, accuracy. The expansion is implemented in dynamically adaptive coherent-state representations, generated by an approach that combines the matching-pursuit algorithm with a gradient-based optimization method. The accuracy and-efficiency-of the resulting propagation method are demonstrated as applied to the canonical model systems introduced by Tully for testing, simulations of dual curve-crossing nonadiabatic dynamics. (c) 2005 American Institute of Physics.