Exact description of excitonic dynamics in molecular aggregates weakly driven by light.

We present a rigorous theoretical description of excitonic dynamics in molecular light-harvesting aggregates photoexcited by weak-intensity radiation of arbitrary properties. While the interaction with light is included up to the second order, the treatment of the excitation–environment coupling is exact and results in an exact expression for the reduced excitonic density matrix that is manifestly related to the spectroscopic picture of the photoexcitation process. This expression takes fully into account the environmental reorganization processes triggered by the two interactions with light. This is particularly important for slow environments and/or strong excitation–environment coupling. Within the exponential decomposition scheme, we demonstrate how our result can be recast as the hierarchy of equations of motion (HEOM) that explicitly and consistently includes the photoexcitation step. We analytically describe the environmental reorganization dynamics triggered by a delta-like excitation of a single chromophore and demonstrate how our HEOM, in appropriate limits, reduces to the Redfield equations comprising a pulsed photoexcitation and the nonequilibrium Forster theory. We also discuss the relation of our formalism to the combined Born–Markov–HEOM approaches in the case of excitation by thermal light.