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

机译:集光系统中的电子相干性和复杂的能量转移动力学

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摘要

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.
机译:我们应用实时路径积分动力学模拟来表征电子相干性在复杂复合体激发能传递(EET)过程中的作用。使用系统浴模型进行分析,该模型展现了光收集网络的基本特征,包括强内部复杂电子耦合和弱内部复杂耦合。众所周知,强复合物内部耦合会产生静态和动态电子相干,这会使激子在多个发色团上离域化,并可能影响复合物EET之间的动力学。利用部分线性化密度矩阵(PLDM)实时路径积分计算得出的数值结果,发现静态和动态相干性都与内部复杂EET的速率相关。为了区分这两种类型的内部复杂相干性对内部复杂EET速率的影响,我们使用多色团Förster共振能量转移(MC-FRET)理论将系统浴模型的原始参数化映射到替代参数化,可以保留静态连贯性的影响,而大大消除动态连贯性的影响。然后表明,模型的两个参数化(即支持动态相干性的原始参数和消除动态相干性的替代方法)在广泛的参数范围内都表现出几乎相同的EET动力学和总体动力学。发现这些观察结果适用于EET供体或受体为二聚体复合物的情况以及二聚体为对称或不对称的情况。这项研究的结果表明,动态相干在复合物EET的实际动力学中仅扮演次要角色,而静态相干在很大程度上控制着光收集网络中非相干复合物EET的动力学。

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