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Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences

Abstract

The observation of persistent oscillatory signals in multidimensional spectra of protein–pigment complexes has spurred a debate on the role of coherence-assisted electronic energy transfer as a key operating principle in photosynthesis. Vibronic coupling has recently been proposed as an explanation for the long lifetime of the observed spectral beatings. However, photosynthetic systems are inherently complicated, and tractable studies on simple molecular compounds are needed to fully understand the underlying physics. In this work, we present measurements and calculations on a solvated molecular homodimer with clearly resolvable oscillations in the corresponding two-dimensional spectra. Through analysis of the various contributions to the nonlinear response, we succeed in isolating the signal due to inter-exciton coherence. We find that although calculations predict a prolongation of this coherence due to vibronic coupling, the combination of dynamic disorder and vibrational relaxation leads to a coherence decay on a timescale comparable to the electronic dephasing time.

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Figure 1: Modelling the linear absorption spectrum of indocarbocyanine.
Figure 2: Effect of energy fluctuations on states A, B and C.
Figure 3: Temporal enhancement of inter-exciton coherence.
Figure 4: Signatures of inter-exciton coherence in two-dimensional spectroscopy.
Figure 5: Decomposition of the different pathways contributing to peak X.

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Acknowledgements

The authors thank V. Prokhorenko, H. Kauffmann and F. Spano for helpful discussions regarding interpretation of the results, and E. Pelletier for assistance with the laser system. Financial support was provided by the Natural Sciences and Engineering Research Council of Canada (to R.S.M., R.J.D.M.) and the Max Planck Society (to R.J.D.M.).

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A.H. and P.J.M.J. performed the measurements. R.T. and T.L.C.J. performed the calculations. A.H., R.T., P.J.M.J. and T.L.C.J. analysed the data. A.H. constructed the experimental set-up. R.S.M. synthesized the compound. A.H. and R.T. wrote the manuscript. R.J.D.M. and J.K. supervised the project.

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Correspondence to R. J. Dwayne Miller.

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Halpin, A., Johnson, P., Tempelaar, R. et al. Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences. Nature Chem 6, 196–201 (2014). https://doi.org/10.1038/nchem.1834

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