Dynamics of a one-dimensional Holstein polaron: The multiconfigurational Ehrenfest method.

Abstract

We have extended the multiconfigurational Ehrenfest (MCE) approach to investigate the dynamics of a one-dimensional Holstein molecular crystal model. It has been shown that the extended MCE approach yields results in perfect agreement with benchmark calculations by the hierarchy equations of motion method. The accuracies of the MCE approach in describing the dynamical properties of the Holstein polaron over a wide range of exciton transfer integrals and exciton-phonon couplings are carefully examined by a detailed comparison with the fully variational multiple Davydov D2 ansatz. It is found that while the MCE approach and the multi-D2 ansatz produce almost exactly the same results for a small transfer integral, the results obtained by the multi-D2 ansatz start to deviate from those by the MCE approach at longer times for a large transfer integral. A large number of coherent state basis functions are required to characterize the delocalized features of the phonon wavefunction in the case of large transfer integral, which becomes computationally too demanding for the multi-D2 ansatz. The MCE approach, on the other hand, uses hundreds to thousands of trajectory guided basis functions and converges very well, thus providing an effective tool for accurate and efficient simulations of polaron dynamics.