Charge transfer as a mechanism for chlorophyll fluorescence concentration quenching

Significance The light-absorbing molecules (chlorophyll) in photosynthetic organisms must be held close together to achieve efficient energy transport but in solution, such close proximity leads to rapid energy loss (quenching). The hypothesized quenching mechanism is photoinduced charge separation followed by rapid charge recombination but this has never been proven. We confirm the feasibility of this mechanism using detailed calculations to show that charge separation outcompetes fluorescence (i.e., induces quenching) at chlorophyll separations compatible with the concentrations at which quenching is observed. Moreover, we reveal that the stiff photosynthetic protein environment inhibits quenching by preventing chlorophyll pairs from adopting a suitable shape for charge transfer. This insight into the protein function identifies a crucial design feature for efficient future artificial light-harvesting devices.

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