苝二酰亚胺二聚体中振动介导的激发转移的几何依赖性
Geometric dependencies of vibronically mediated excitation transfer in rylene dyads
AI总结：
本研究通过光谱实验和振动二聚体模型，揭示了苝二酰亚胺二聚体中激发转移对几何排列的依赖，涵盖Förster输运与强耦合机制。
摘要：
我们利用吸收光谱、荧光光谱和瞬态吸收光谱研究了苝二酰亚胺二聚体在不同几何排列下的激发转移。瞬态吸收的偏振和探测频率依赖性追踪了二聚体内转移与振动弛豫之间的相互作用。我们解析了苝二酰亚胺之间分子间耦合的微观参数化，并再现了输运数据。分子几何结构的动态采样捕获了热涨落，用于正交排列二聚体的耦合的量子化学估计，其中静态估计为零，而简正模式分析对涨落的低估达一个数量级。非微扰处理通过振动二聚体模型提供了对强耦合非谐振动模式调制输运的描述。振动动力学被证明涵盖了正交排列二聚体的Förster输运机制和平行发色团的强耦合机制，并使我们能够模拟信号随探测频率的变化。
英文摘要：
We study the excitation transfer in various geometric arrangements of rylene dimers using absorption, fluorescence and transient absorption spectra. Polarization and detection frequency dependencies of transient absorption track the interplay of transfer and vibrational relaxation within the dyads. We have resolved microscopic parametrization of intermolecular coupling between rylenes and reproduced transport data. Dynamical sampling of molecular geometries captures thermal fluctuations for Quantum Chemical estimate of couplings for orthogonally arranged dyad, where static estimates vanish and normal mode analysis of fluctuations underestimates them by an order of magnitude. Nonperturbative accounts for the modulation of transport by strongly coupled anharmonic vibrational modes is provided by a vibronic dimer model. Vibronic dynamics is demonstrated to cover both the Förster transport regime of orthogonally arranged dyads and the strong coupling regime of parallel chromophores and allows us to model signal variations along the detection frequency.
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