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Elucidation of the timescales and origins of quantum electronic coherence in LHCII

Nature Chemistry volume 4, pages 389–395 (2012)Cite this article

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Abstract

Photosynthetic organisms harvest sunlight with near unity quantum efficiency. The complexity of the electronic structure and energy transfer pathways within networks of photosynthetic pigment–protein complexes often obscures the mechanisms behind the efficient light-absorption-to-charge conversion process. Recent experiments, particularly using two-dimensional spectroscopy, have detected long-lived quantum coherence, which theory suggests may contribute to the effectiveness of photosynthetic energy transfer. Here, we present a new, direct method to access coherence signals: a coherence-specific polarization sequence, which isolates the excitonic coherence features from the population signals that usually dominate two-dimensional spectra. With this polarization sequence, we elucidate coherent dynamics and determine the overall measurable lifetime of excitonic coherence in the major light-harvesting complex of photosystem II. Coherence decays on two distinct timescales of 47 fs and ~800 fs. We present theoretical calculations to show that these two timescales are from weakly and moderately strongly coupled pigments, respectively.

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Figure 1: Absolute-value non-rephasing spectra under coherence-specific polarization at 77 K.
Figure 2: Integrated, absolute-value relaxation spectra taken under coherence-specific polarization plotted versus waiting time.
Figure 3: Simulations of decay curves for coherence elements of the density matrix between pairs of excitons within monomeric LHCII.

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Acknowledgements

This work was supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy (contract DE-AC02-05CH11231) and the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US Department of Energy (grant DE-AC03-76SF000098) (at LBNL and University of California, Berkeley). R.B. and M.B. acknowledge EU project PITN-GA-2009-238017 HARVEST and EU project 245070 FP7-KBBE-2009-3SUNBIOPATH. G.S.S.-C. thanks the A.A.U.W. American Fellowship and N.S.G. thanks the LBNL Glenn T. Seaborg postdoctoral fellowship for support.

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Author notes

  1. Gabriela S. Schlau-Cohen, Akihito Ishizaki & Tessa R. Calhoun

    Present address: Present address: Department of Chemistry, Stanford University, Stanford, California 94305, USA (G.S.S-C.), Institute for Molecular Science, National Institutes of Natural Sciences, Okazaki 444-8585, Japan (A.I.), Lewis-Sigler Institue for Integrative Genomics, Princeton University, Princeton, New Jersey 08544, USA (T.R.C.),

Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, 94720, California, USA

    Gabriela S. Schlau-Cohen, Akihito Ishizaki, Tessa R. Calhoun, Naomi S. Ginsberg & Graham R. Fleming

  2. Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, 94720, California, USA

    Gabriela S. Schlau-Cohen, Akihito Ishizaki, Tessa R. Calhoun, Naomi S. Ginsberg & Graham R. Fleming

  3. Dipartimento di Biotecnologie, Facoltà di Scienze, Università di Verona, Strada Le Grazie, I-37134, Verona, Italia

    Matteo Ballottari & Roberto Bassi

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Contributions

G.S.S.-C. and G.R.F. conceived and designed the experiments. G.S.S.-C., T.R.C. and N.S.G. performed the experiments. G.S.S.-C. and A.I. analysed the data. A.I. performed theoretical calculations. M.B. and R.B. grew and purified the sample. G.S.S.-C. and A.I. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Graham R. Fleming.

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Schlau-Cohen, G., Ishizaki, A., Calhoun, T. et al. Elucidation of the timescales and origins of quantum electronic coherence in LHCII. Nature Chem 4, 389–395 (2012). https://doi.org/10.1038/nchem.1303

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