论文标题
分子聚集体中的激发动力学的精确描述，弱驱动光
Exact description of excitonic dynamics in molecular aggregates weakly driven by light
论文作者
论文摘要
我们提出了对分子光收获聚集体中激素动力学的严格理论描述，该聚集体通过任意特性的弱强度辐射进行了光激励。虽然与光的相互作用包括到第二阶，但精确的激发 - 环境耦合的处理是准确的，并且导致降低的激子密度矩阵的精确表达，这显然与光激发过程的光谱图相关。该表达式充分考虑了两种与光的相互作用触发的环境重组过程。这对于缓慢的环境和/或强烈的激发环境耦合尤其重要。在指数分解方案中，我们演示了如何将结果重塑为运动方程（HEOM）的层次结构，这些方程式（HEOM）明确且一致地包括光激发步骤。我们分析描述了单个发色团的三角样激励触发的环境重组动力学，并证明我们的HEOM在适当的限制下如何减少包括脉冲光激发和非平衡性福特斯特理论的Redfield方程。我们还讨论了形式主义与热光激发的情况下的Born-Markov-Heom方法的关系。
We present a rigorous theoretical description of excitonic dynamics in molecular light-harvesting aggregates photoexcited by weak-intensity radiation of arbitrary properties. While the interaction with light is included up to the second order, the treatment of the excitation-environment coupling is exact and results in an exact expression for the reduced excitonic density matrix that is manifestly related to the spectroscopic picture of the photoexcitation process. This expression takes fully into account the environmental reorganization processes triggered by the two interactions with light. This is particularly important for slow environments and/or strong excitation-environment coupling. Within the exponential decomposition scheme, we demonstrate how our result can be recast as the hierarchy of equations of motion (HEOM) that explicitly and consistently includes the photoexcitation step. We analytically describe the environmental reorganization dynamics triggered by a delta-like excitation of a single chromophore, and demonstrate how our HEOM, in appropriate limits, reduces to the Redfield equations comprising a pulsed photoexcitation and the nonequilibrium Foerster theory. We also discuss the relation of our formalism to the combined Born-Markov-HEOM approaches in the case of excitation by thermal light.
