Imaginary-time open-chain path-integral approach for two-state time correlation functions and applications in charge transfer

Abstract

Quantum time correlation functions (TCFs) involving two states are important for describing nonadiabatic dynamical processes such as charge transfer (CT). Based on a previous single-state method, we propose an imaginary-time open-chain path-integral (OCPI) approach for evaluating the two-state symmetrized TCFs. Expressing the forward and backward propagation on different electronic potential energy surfaces as a complex-time path integral, we then transform the path variables to average and difference variables such that the integration over the difference variables up to the second order can be performed analytically. The resulting expression for the symmetrized TCF is equivalent to sampling the open-chain configurations in an effective potential that corresponds to the average surface. Using importance sampling over the extended OCPI space via open path-integral molecular dynamics, we tested the resulting path-integral approximation by calculating the Fermi’s golden rule CT rate constant within a widely used spin-boson model. Comparing with the real-time linearized semiclassical method and analytical result, we show that the imaginary-time OCPI provides an accurate two-state symmetrized TCF and rate constant in the typical turnover region. It is shown that the first bead of the open chain corresponds to physical zero-time and that the endpoint bead corresponds to final time t; oscillations of the end-to-end distance perfectly match the nuclear mode frequency. The two-state OCPI scheme is seen to capture the tested model’s electronic quantum coherence and nuclear quantum effects accurately.