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Coherent-potential-approximation study of excitonic absorption in orientationally disordered molecular aggregates

机译:相似势阱近似研究激子吸收   取向无序的分子聚集体

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摘要

We study the dynamics of a single Frenkel exciton in a disordered molecularchain. The coherent-potential approximation (CPA) is applied to the situationwhen the single-molecule excitation energies as well as the transition dipolemoments, both their absolute values and orientations, are random. Such model isbelieved to be relevant for the description of the linear optical properties ofone-dimensional $J$ aggregates. We calculate the exciton density of states, thelinear absorption spectra and the exciton coherence length which reveals itselfin the linear optics. A detailed analysis of the low-disorder limit of thetheory is presented. In particular, we derive asymptotic formulas relating theabsorption linewidth and the exciton coherence length to the strength ofdisorder. Such expressions account simultaneously for all the above types ofdisorder and reduce to well-established form when no disorder in the transitiondipoles is present. The theory is applied to the case of purely orientationaldisorder and is shown to agree well with exact numerical diagonalization.
机译:我们研究了无序分子链中单个Frenkel激子的动力学。相干势近似(CPA)适用于单分子激发能以及跃迁偶极矩(其绝对值和方向都随机)的情况。认为这种模型与一维$ J $聚集体的线性光学性质的描述有关。我们计算出态的激子密度,线性吸收光谱和激子相干长度,这可以在线性光学中揭示出来。给出了对理论下限的详细分析。特别是,我们得出了将吸收线宽和激子相干长度与无序强度联系起来的渐近公式。这样的表达同时解决了所有上述类型的障碍,并且当过渡偶极子中不存在紊乱时,这种表达减少为公认的形式。该理论适用于纯粹取向混乱的情况,并被证明与精确的数值对角化很好地吻合。

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