A molecular theory of the line shape : inhomogeneous and homogeneous electronic spectra of dilute chromophores in nonpolar fluids
A molecular theory of the line shape : inhomogeneous and homogeneous electronic spectra of dilute chromophores in nonpolar fluids
复制标题
线形的分子理论：非极性流体中稀发色团的不均匀和均匀电子光谱
DOI：
10.1063/1.466092
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发表时间：
1993
影响因子：
4.4
通讯作者：
J. Skinner
中科院分区：
文献类型：
--
作者：
J. Saven;J. Skinner
久保的谱线形状随机理论为非均匀展宽和均匀展宽以及两者之间的过渡提供了一种优雅的现象学描述。这一理论已在许多实验的分析中得到了有益的应用。在本文中，我们试图通过发展一个完整的线形分子理论，为Kubo模型提供一个微观基础。为了确定，我们主要研究非极性流体中稀发色团的光学线形。Kubo理论的许多特征都在分子理论中找到；事实上，分子理论给出了涉及Kubo唯象参数的溶剂结构和动力学的微观表达式，并为随机理论中的高斯假设提供了一些理由。另一方面，与久保理论的指数假设相反，分子理论给出了一个明显非指数的跃迁频率时间关联函数，并发现这是一种非指数的时间相关函数。
Kubo’s stochastic theory of the spectral line shape provides an elegant phenomenological description of inhomogeneous and homogeneous broadening and the transition between the two. This theory has been used profitably in the analysis of many experiments. In this paper we attempt to provide a microscopic foundation for the Kubo model by developing a completely molecular theory of the line shape. For definiteness we focus on the optical line shape of dilute chromophores in nonpolar fluids. Many of the features of the Kubo theory are found in the molecular theory; indeed, the molecular theory produces microscopic expressions involving the solvent structure and dynamics for Kubo’s phenomenological parameters, and provides some justification for the Gaussian assumption in the stochastic theory. On the other hand, the molecular theory produces a transition frequency time‐correlation function that is distinctly nonexponential, in contrast to the exponential assumption of the Kubo theory, and it is found that thi...