Distinguishing the roles of energy funnelling and delocalization in photosynthetic light harvesting

TL;DR

This paper investigates the roles of energy funnelling and excitonic delocalization in photosynthetic light harvesting, concluding that energy funnelling is the primary factor while delocalization has a minor, sometimes detrimental, effect.

Contribution

The study introduces a method to distinguish the effects of energy funnelling and delocalization by comparing natural and counterfactual models in photosynthesis.

Findings

Energy funnelling is the main driver of efficient energy transfer.

Supertransfer from delocalization provides only a minor enhancement.

Delocalization is likely a side-effect, not an adaptive feature.

Abstract

Photosynthetic complexes improve the transfer of excitation energy from peripheral antennas to reaction centers in several ways. In particular, a downward energy funnel can direct excitons in the right direction, while coherent excitonic delocalization can enhance transfer rates through the cooperative phenomenon of supertransfer. However, isolating the role of purely coherent effects is difficult because any change to the delocalization also changes the energy landscape. Here, we show that the relative importance of the two processes can be determined by comparing the natural light-harvesting apparatus with counterfactual models in which the delocalization and the energy landscape are altered. Applied to the example of purple bacteria, our approach shows that although supertransfer does enhance the rates somewhat, the energetic funnelling plays the decisive role. Because delocalization has a minor role (and is sometimes detrimental), it is most likely not adaptive, being a side-effect of the dense chlorophyll packing that evolved to increase light absorption per reaction center.