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Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting

Nature Chemistry volume 4, pages 396–404 (2012)Cite this article

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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.

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Figure 1: Structural model and measurements of PE545.
Figure 2: Broadband excitation of PE545.
Figure 3: Difference spectra highlighting the oscillating signal amplitude.
Figure 4: Structural model and measurements of HT–CpcA–PEB.
Figure 5: Simulated energy trajectories and absorption lineshapes.

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Acknowledgements

This work was supported by the Natural Sciences and Engineering Research Council of Canada, the US Air Force Office of Scientific Research (FA9550-10-1-0260) and DARPA (QuBE, G.D.S.), the Australian Research Council (P.M.G.C.) and by grants from the US National Science Foundation (MCB-0519743 and MCB-1021725 to D.A.B.). P. Brumer, R. Kapral and R. Dinshaw are thanked for discussions.

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Authors and Affiliations

  1. Department of Chemistry, Institute for Optical Sciences and Centre for Quantum Information and Quantum Control, University of Toronto, 80 St. George Street, Toronto, M5S 3H6, Ontario, Canada

    Cathy Y. Wong, Daniel B. Turner & Gregory D. Scholes

  2. Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, 16802, Pennsylvania, USA

    Richard M. Alvey & Donald A. Bryant

  3. School of Physics and Centre for Applied Medical Research, St. Vincent's Hospital, The University of New South Wales, Sydney, NSW 2052, Australia

    Krystyna E. Wilk & Paul M. G. Curmi

  4. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Robert J. Silbey

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Contributions

C.Y.W. performed all spectroscopic experiments and data analysis except those reported in Fig. 2. D.B.T. performed the experiments reported in Fig. 2. R.M.A. and D.A.B. prepared and purified the CpcA–PEB protein. K.E.W. and P.M.G.C. cultured the Rhodomonas CS24 algae and isolated and purified the PE545 antenna protein. G.D.S. performed the quantum-classical calculations of the exciton states and, with R.J.S., interpreted the correlation phenomena. C.Y.W. and G.D.S. wrote the paper and planned the research. All authors commented on the manuscript.

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Correspondence to Gregory D. Scholes.

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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

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