We report two-dimensional electronic spectroscopy (2DES) experiments on the bacterial reaction center (BRC) from purple bacteria, revealing hidden vibronic and excitonic structure. Through analysis of the coherent dynamics of the BRC, we identify multiple quasi-resonances between pigment vibrations and excitonic energy gaps, and vibronic coherence transfer processes that are typically neglected in standard models of photosynthetic energy transfer and charge separation. We support our assignment with control experiments on bacteriochlorophyll and simulations of the coherent dynamics using a reduced excitonic model of the BRC. We find that specific vibronic coherence processes can readily reveal weak exciton transitions. While the functional relevance of such processes is unclear, they provide a spectroscopic tool that uses vibrations as a window for observing excited state structure and dynamics elsewhere in the BRC via vibronic coupling. Vibronic coherence transfer reveals the upper exciton of the “special pair” that was weakly visible in previous 2DES experiments.

Biosciences Division Argonne National Laboratory Argonne IL 60439 USA

Department of Chemistry University of California Riverside CA 92521 USA

Department of Chemistry Washington University St Louis MO 63130 USA

Department of Physics University of Michigan 450 Church St Ann Arbor MI 48109 USA

Faculty of Mathematics and Physics Charles University Ke Karlovu 5 CZ 12116 Prague 2 Czech Republic

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