Efficiency of energy funneling in the photosystem II supercomplex of higher plants

The investigation of energy transfer properties in photosynthetic multi-protein networks gives insight into their underlying design principles. Here, we discuss the excitonic energy transfer mechanisms of the photosystem II (PS-II) C₂S₂M₂ supercomplex, which is the largest isolated functional unit of the photosynthetic apparatus of higher plants. Despite the lack of a definite energy gradient in C₂S₂M₂, we show that the energy transfer is directed by relaxation to low energy states. C₂S₂M₂ is not organized to form pathways with strict energetically downhill transfer, which has direct consequences for the transfer efficiency, transfer pathways and transfer limiting steps. The exciton dynamics is sensitive to small changes in the energetic layout which, for instance, are induced by the reorganization of vibrational coordinates. In order to incorporate the reorganization process in our numerical simulations, we go beyond rate equations and use the hierarchically coupled equation of motion approach (HEOM). While transfer from the peripheral antenna to the proteins in proximity to the reaction center occurs on a faster time scale, the final step of the energy transfer to the RC core is rather slow, and thus the limiting step in the transfer chain. Our findings suggest that the structure of the PS-II supercomplex guarantees photoprotection rather than optimized efficiency.