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Exciton coherence length fluctuations in chromophore aggregates probed by multidimensional optical spectroscopy

机译:多维光谱法探测发色团聚集体的激子相干长度波动

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摘要

The coherent third order optical response of molecular aggregates with fluctuating frequencies, couplings, and transition dipole moments is studied. We derived stochastic nonlinear exciton equations (SNEEs) by combining the quasiparticle picture of excitons with the path integral over stochastic bath paths described by the stochastic Liouville equations. Coherent two-dimensional (2D) spectra are calculated for a tetramer model system whose transition dipole orientations undergo two-state stochastic jumps on an arbitrary timescale. Correspondence between domains of ordered dipoles, which determine the exciton coherence length and the absorption peaks, is established. Signatures of domain coherence length fluctuations are observed in the cross peak dynamics of the 2D spectra in specific pulse polarization configurations.
机译:研究了具有波动频率,耦合和跃迁偶极矩的分子聚集体的相干三阶光学响应。通过将激子的准粒子图与随机Liouville方程所描述的随机浴路径上的路径积分相结合,得出了随机非线性激子方程(SNEE)。为四聚体模型系统计算了相干的二维(2D)光谱,该系统的过渡偶极子取向在任意时间尺度上经历了两态随机跳跃。建立了确定激子相干长度和吸收峰的有序偶极子畴之间的对应关系。在特定脉冲极化配置中的2D光谱的交叉峰动态中观察到域相干长度波动的特征。

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