Photosynthesis powers life on our planet. The basic photosynthetic architecture consists of antenna complexes that harvest solar energy and reaction centres that convert the energy into stable separated charge. In oxygenic photosynthesis, the initial charge separation occurs in the photosystem II reaction centre, the only known natural enzyme that uses solar energy to split water. Both energy transfer and charge separation in photosynthesis are rapid events with high quantum efficiencies. In recent nonlinear spectroscopic experiments, long-lived coherences have been observed in photosynthetic antenna complexes, and theoretical work suggests that they reflect underlying electronic–vibrational resonances, which may play a functional role in enhancing energy transfer. Here, we report the observation of coherent dynamics persisting on a picosecond timescale at 77 K in the photosystem II reaction centre using two-dimensional electronic spectroscopy. Supporting simulations suggest that the coherences are of a mixed electronic–vibrational (vibronic) nature and may enhance the rate of charge separation in oxygenic photosynthesis.
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F.D.F., J.P. and J.P.O. acknowledge support from the Office of Basic Energy Sciences, the US Department of Energy (grant no. DE-FG02-07ER15904). S.S.S. acknowledges support from the National Science Foundation (grant no. PHY-0748470). D.E.W. acknowledges support from the Center for Solar and Thermal Energy Conversion (CSTEC), an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (award no. DE-SC0000957). A.G., V.B., L.V. and D.A. acknowledge support from the Research Council of Lithuania (LMT grant no. MIP-069/2012).
The authors declare no competing financial interests.
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Fuller, F., Pan, J., Gelzinis, A. et al. Vibronic coherence in oxygenic photosynthesis. Nature Chem 6, 706–711 (2014). https://doi.org/10.1038/nchem.2005
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