Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvest
Author: ["Cathy Y. Wong","Richard M. Alvey","Daniel B. Turner","Krystyna E. Wilk","Donald A. Bryant","Paul M. G. Curmi","Robert J. Silbey","Gregory D. Scholes"]
Publication: Nature Chemistry
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Abstract
The effective absorption cross-section of a molecule (acceptor) can be greatly increased by associating it with a cluster of molecules that absorb light and transfer the excitation energy to the acceptor molecule. The basic mechanism of such light harvesting by Förster resonance energy transfer (FRET) is well established, but recent experiments have revealed a new feature whereby excitation is coherently shared among donor and acceptor molecules during FRET. In the present study, two-dimensional electronic spectroscopy was used to examine energy transfer at ambient temperature in a naturally occurring light-harvesting protein (PE545 of the marine cryptophyte alga Rhodomonas sp. strain CS24). Quantum beating was observed across a range of excitation frequencies. The shapes of those features in the two-dimensional spectra were examined. Through simulations, we show that two-dimensional electronic spectroscopy provides a probe of the adiabaticity of the free energy landscape underlying light harvesting. Quantum beating has been observed in photosynthetic systems, suggesting that energy-transfer processes in natural light harvesting could involve quantum effects. Now, extensive beating is found in the light-harvesting protein of a cryptophyte alga, and shown to be electronic. The implications of these observations on the free-energy surfaces and exciton delocalization were investigated.
Cite this article
Wong, C., Alvey, R., Turner, D. et al. Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting. Nature Chem 4, 396–404 (2012). https://doi.org/10.1038/nchem.1302
