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Issue 46, 2015
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Electronic coherence and the kinetics of inter-complex energy transfer in light-harvesting systems

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Abstract

We apply real-time path-integral dynamics simulations to characterize the role of electronic coherence in inter-complex excitation energy transfer (EET) processes. The analysis is performed using a system-bath model that exhibits the essential features of light-harvesting networks, including strong intra-complex electronic coupling and weak inter-complex coupling. Strong intra-complex coupling is known to generate both static and dynamic electron coherences, which delocalize the exciton over multiple chromophores and potentially influence the inter-complex EET dynamics. With numerical results from partial linearized density matrix (PLDM) real-time path-integral calculations, it is found that both static and dynamic coherence are correlated with the rate of inter-complex EET. To distinguish the impact of these two types of intra-complex coherence on the rate of inter-complex EET, we use Multi-Chromophore Förster Resonance Energy Transfer (MC-FRET) theory to map the original parameterization of the system-bath model to an alternative parameterization for which the effects of static coherence are preserved while the effects of dynamic coherence are largely eliminated. It is then shown that both parameterizations of the model (i.e., the original that supports dynamic coherence and the alternative that eliminates it), exhibit nearly identical EET kinetics and population dynamics over a wide range of parameters. These observations are found to hold for cases in which either the EET donor or acceptor is a dimeric complex and for cases in which the dimeric complex is either symmetric or asymmetric. The results from this study suggest that dynamic coherence plays only a minor role in the actual kinetics of inter-complex EET, whereas static coherence largely governs the kinetics of incoherent inter-complex EET in light-harvesting networks.

Graphical abstract: Electronic coherence and the kinetics of inter-complex energy transfer in light-harvesting systems

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Publication details

The article was received on 30 Apr 2015, accepted on 01 Jun 2015 and first published on 01 Jun 2015


Article type: Paper
DOI: 10.1039/C5CP02517F
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Phys. Chem. Chem. Phys., 2015,17, 30914-30924
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    Electronic coherence and the kinetics of inter-complex energy transfer in light-harvesting systems

    P. Huo and T. F. Miller III, Phys. Chem. Chem. Phys., 2015, 17, 30914
    DOI: 10.1039/C5CP02517F

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

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