Accessing dark states optically through excitation-ferrying states

Abstract

The efficiency of solar energy harvesting systems is largely determined by their ability to transfer excitations from the antenna to the energy trapping center before recombination. Dark state protection, achieved by coherent coupling between subunits in the antenna structure, can significantly reduce radiative recombination and enhance the efficiency of energy trapping. Because the dark states cannot be populated by optical transitions from the ground state, they are usually accessed through phononic relaxation from the bright states. In this study, we explore a novel way of connecting the dark states and the bright states via optical transitions. In a ring-like chromophore system inspired by natural photosynthetic antennae, the single-excitation bright state can be optically connected to the lowest energy single-excitation dark state through certain double-excitation states. We call such double-excitation states the ferry states and show that they are the result of accidental degeneracy between two categories of double-excitation states. We then mathematically prove that the ferry states are only available when N, the number of subunits on the ring, satisfies N=4l+2 (l being an integer). Numerical calculations confirm that the ferry states enhance the energy transfer power of our model, showing a significant energy transfer power spike at N=6 compared with smaller N values, even without phononic relaxation. The proposed mathematical theory for the ferry states is not restricted to this one particular system or numerical model. In fact, it is potentially applicable to any coherent optical system that adopts a ring-shaped chromophore arrangement. Beyond the ideal case, the ferry state mechanism also demonstrates robustness under weak phononic dissipation, weak site energy disorder, and large coupling strength disorder.