Multiple time scale open systems: Reaction rates and quantum coherence in model retinal photoisomerization under incoherent excitation

Abstract

Many important open quantum systems, such as light harvesting systems irradiated with natural incoherent light, present challenging computational problems. Specifically, such systems are characterized by multiple time scales over many orders of magnitude. We describe and apply an efficient approach to determine rates and dynamics in such systems. As an example, we present a theoretical and computational analysis of retinal isomerization under incoherent solar excitation using a minimal retinal model. Solar- and bath-induced Fano coherences are shown to have a small but non-negligible effect on the reaction dynamics, and the effect of Fano coherences on the reaction rate is shown to depend strongly upon the form and strength of the system-bath coupling. Using the isomerization probability to obtain the time-dependent cellular hyperpolarization, we show that the effect of coherence on hyperpolarization dynamics is small compared to the effect of natural variations in the solar intensity.