Polaron dynamics with off-diagonal coupling: beyond the Ehrenfest approximation

Abstract

Treated traditionally by the Ehrenfest approximation, the dynamics of a one-dimensional molecular crystal model with off-diagonal exciton–phonon coupling is investigated in this work using the Dirac–Frenkel time-dependent variational principle with the multi-D₂Ansatz. It is shown that the Ehrenfest method is equivalent to our variational method with the single D₂Ansatz, and with the multi-D₂Ansatz, the accuracy of our simulated dynamics is significantly enhanced in comparison with the semi-classical Ehrenfest dynamics. The multi-D₂Ansatz is able to capture numerically accurate exciton momentum probability and help clarify the relation between the exciton momentum redistribution and the exciton energy relaxation. The results demonstrate that the exciton momentum distributions in the steady state are determined by a combination of the transfer integral and the off-diagonal coupling strength, independent of the excitonic initial conditions. We also probe the effect of the transfer integral and the off-diagonal coupling on exciton transport in both real and reciprocal space representations. Finally, the variational method with importance sampling is employed to investigate temperature effects on exciton transport using the multi-D₂Ansatz, and it is demonstrated that the variational approach is valid in both low and high temperature regimes.