Design Principles for Long-Range Energy Transfer at Room Temperature

Abstract

Under physiological conditions, ballistic long-range transfer of electronic excitations in molecular aggregates is generally expected to be suppressed by noise and dissipative processes. Hence, quantum phenomena are not considered to be relevant for the design of efficient and controllable energy transfer over significant length scales and timescales. Contrary to this conventional wisdom, here we show that the robust quantum properties of small configurations of repeating clusters of molecules can be used to tune energy-transfer mechanisms that take place on much larger scales. With the support of an exactly solvable model, we demonstrate that coherent exciton delocalization and dark states within unit cells can be used to harness dissipative phenomena of varying nature (thermalization, fluorescence, nonradiative decay, and weak intersite correlations) to support classical propagation over macroscopic distances. In particular, we argue that coherent delocalization of electronic excitations over just a few pigments can drastically alter the relevant dissipation pathways that influence the energy-transfer mechanism and thus serve as a molecular control tool for large-scale properties of molecular materials. Building on these principles, we use extensive numerical simulations to demonstrate that they can explain currently not-understood measurements of micron-scale exciton diffusion in nanofabricated arrays of bacterial photosynthetic complexes. Based on these results, we provide quantum design guidelines at the molecular scale to optimize both energy-transfer speed and range over macroscopic distances in artificial light-harvesting architectures.