Memory effects in the efficiency control of energy transfer under incoherent light excitation in noisy environments

Abstract

Fluctuations in energy gap and coupling constants between chromophores can play an important role in absorption and energy transfer across a collection of two-level systems. In photosynthesis, light-induced quantum coherence can affect the efficiency of energy transfer to the designated “trap” state. Theoretically, the interplay between fluctuations and coherence has been studied often, employing either a Markovian or a perturbative approximation. In this study, we depart from these approaches to incorporate memory effects by using Kubo’s quantum stochastic Liouville equation. We introduce the effects of decay of the created excitation (to the ground state) on the desired propagation and trapping that provides a direction of flow of the excitation. In the presence of light-induced pumping, we establish a relation between the efficiency, the mean survival time, and the correlation decay time of the bath-induced fluctuations. A decrease in the steady-state coherence during the transition from the non-Markovian regime to the Markovian limit results in a decrease in efficiency. As in the well-known Haken–Strobl model, the ratio of the square of fluctuation strength to the rate plays a critical role in determining the mechanism of energy transfer and in shaping the characteristics of the efficiency profile. We recover a connection between the transfer flux and the imaginary part of coherences in both equilibrium and excited bath states, in both correlated and uncorrelated bath models. We uncover a non-monotonic dependence of efficiency on site energy heterogeneity for both correlated and uncorrelated bath models.