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arXiv 2603.04483cond-mat.mes-hallphysics.chem-phquant-ph
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在分子聚集体中考虑受激子-受激子湮灭的相干双激子传输

Coherent Biexciton Transport in the Presence of Exciton-Exciton Annihilation in Molecular Aggregates

University of Nevada, Las Vegas(内华达大学拉斯维加斯分校)

Rajesh Dutta, Chern Chuang

AI总结:

研究了分子聚集体中双激子动力学,探讨初始态相干性及动量组成对荧光衰减和传输的影响,揭示了相干传输与非相干弛豫的区别及内部转换过程的重要性。

摘要:

我们提出了一种理论框架,用于描述分子聚集体中双激子动力学,该框架在减少密度矩阵形式中明确处理了激发态之间的人口和相干性。通过扩展动力学描述,超越弱耦合极限,该方法捕捉了激子局域化和激子-激子湮灭的影响,同时保持在马尔可夫描述下的计算可行性。利用该框架,我们研究了初始双激子态的空间分布和动量组成如何影响荧光衰减和传输。非相干初始条件导致强非指数弛豫和由非线性人口动力学驱动的时间依赖扩散。相比之下,相干准备的双激子态表现出明显的早期相干传输,其特性取决于初始态是否作为单激子态的驻波或行波叠加态。尽管J和H聚集体的近似相同发射动力学,双激子传输特性却因带结构依赖的干涉效应显著不同。我们的结果表明,双激子动力学仍强烈受初始态相干性和动量组成的影响。除了初始态制备外,相干到非相干的过渡以及激子密度的扩散也对内部转换过程如激子融合和衰减到第一激发态敏感。本工作确立了初始态制备作为许多激子传输在激子系统中的关键控制参数,并提供了一个解释非线性光学实验的通用框架,超越基于人口描述的框架。

英文摘要:

We present a theoretical framework for biexciton dynamics in molecular aggregates that explicitly treats populations and coherences across excitation manifolds within a reduced density-matrix formalism. By extending kinetic descriptions beyond the weak-coupling limit, the approach captures the influence of exciton delocalization and exciton-exciton annihilation while remaining computationally tractable within a Markovian description of environmental relaxation. Using this framework, we investigate how the spatial profile and momentum composition of the initial biexciton state govern fluorescence decay and transport. Incoherent initial conditions lead to strongly non-exponential relaxation and time-dependent diffusion driven by nonlinear population kinetics. In contrast, coherently prepared biexciton states exhibit pronounced early-time coherent transport, whose character depends sensitively on whether the initial state is prepared as a standing-wave or traveling-wave superposition of single-exciton modes. Despite nearly identical emission dynamics for J and H aggregate, biexciton transport properties differ markedly due to band structure-dependent interference effect. Our results demonstrate that biexciton dynamics remains strongly influenced by initial-state coherence and momentum composition. Besides initial-state preparation, the coherent-to-incoherent crossover and the diffusive spreading of the exciton density are sensitive to internal conversion processes such as exciton fusion and the decay to the first excited state. The present work establishes initial-state preparation as a key control parameter for many-exciton transport in excitonic systems and provides a general framework for interpreting nonlinear optical experiments beyond population-based descriptions.

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