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Identification and characterization of diverse coherences in the Fenna–Matthews–Olson complex

Abstract

The idea that excitonic (electronic) coherences are of fundamental importance to natural photosynthesis gained popularity when slowly dephasing quantum beats (QBs) were observed in the two-dimensional electronic spectra of the Fenna–Matthews–Olson (FMO) complex at 77 K. These were assigned to superpositions of excitonic states, a controversial interpretation, as the strong chromophore–environment interactions in the complex suggest fast dephasing. Although it has been pointed out that vibrational motion produces similar spectral signatures, a concrete assignment of these oscillatory signals to distinct physical processes is still lacking. Here we revisit the coherence dynamics of the FMO complex using polarization-controlled two-dimensional electronic spectroscopy, supported by theoretical modelling. We show that the long-lived QBs are exclusively vibrational in origin, whereas the dephasing of the electronic coherences is completed within 240 fs even at 77 K. We further find that specific vibrational coherences are produced via vibronically coupled excited states. The presence of such states suggests that vibronic coupling is relevant for photosynthetic energy transfer.

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Fig. 1: Structure and absorption of the FMO complex
Fig. 2: Polarization-controlled 2DES of the FMO complex
Fig. 3: Selected QBs in FMO.
Fig. 4: Oscillation maps.

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Acknowledgements

The work in Lund was supported by the Swedish Research Council, the Knut and Alice Wallenberg Foundation and the Crafoord Foundation. R.T. acknowledges The Netherlands Organisation for Scientific Research (NWO) for support through a Rubicon grant. D.B. acknowledges funding from Czech Science Foundation under grant no. P501/12/G055 and institutional support RVO:60077344. We thank D. Paleček for making available his code for complex QB analysis.

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D.Z. conceived the idea, E.T., M.J.P.A., K.Z. and D.Z. designed and performed experiments, R.T., J.K. and T.L.C.J. designed the theory, R.T. performed simulations and D.B. extracted and purified the sample. E.T., M.J.P.A. and R.T. analysed the data. E.T., R.T. and D.Z. wrote the manuscript with input from all the other authors.

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Correspondence to Donatas Zigmantas.

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Supplementary Figures 1–5, Supplementary Table 1, Supplementary Data and Methods

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Thyrhaug, E., Tempelaar, R., Alcocer, M.J.P. et al. Identification and characterization of diverse coherences in the Fenna–Matthews–Olson complex. Nature Chem 10, 780–786 (2018). https://doi.org/10.1038/s41557-018-0060-5

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