Correlated intermolecular coupling fluctuations in photosynthetic complexes

The functioning and efficiency of natural photosynthetic complexes is strongly influenced by their embedding in a noisy protein environment, which can even serve to enhance the transport efficiency. Interactions with the environment induce fluctuations of the transition energies and couplings between the chlorophyll molecules, and due to the fact that different fluctuations will partially be caused by the same environmental factors, correlations between the various fluctuations will occur. We argue that fluctuations of the couplings should, in general, not be neglected, as these have a considerable impact on population transfer rates, decoherence rates, and the efficiency of photosynthetic complexes. Furthermore, while correlations between transition energy fluctuations have been studied, we provide the first quantitative study of the effect of correlations between coupling fluctuations and transition energy fluctuations, and of correlations between the various coupling fluctuations. It is shown that these additional correlations typically lead to changes in interchromophore transfer rates and population oscillations and can lead to a limited enhancement of the light harvesting efficiency.