Time resolved polarization spectroscopy: Level kinetics and rotational diffusion
Time resolved polarization spectroscopy: Level kinetics and rotational diffusion
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DOI：
10.1063/1.444684
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发表时间：
1983-06
影响因子：
4.4
通讯作者：
A. Cross;D. Waldeck;G. Fleming
中科院分区：
文献类型：
--
作者：
A. Cross;D. Waldeck;G. Fleming
时间分辨偏振光谱是研究液体动力学的一种有效而灵敏的技术。利用这一技术，可以获得有关溶液中各种驰豫过程的信息，包括处于不同电子态的分子的运动，以及这些态之间的跃迁。由于实验通常同时测量电子驰豫和分子重定向，观察到的信号可以具有复杂的形式，表示这两种效应的耦合，其方式取决于给定系统中存在的特定衰变过程方案。假设分子运动用非对称旋转扩散来描述，我们给出了一种通用算法，用于推导具有这些现象的系统的任意方案的实验信号的形式。文中给出了几个算例，并用推导出的公式解释了实验结果，包括以下情况：(1)激发态扩散张量为零。
Time resolved polarization spectroscopy is a powerful and sensitive technique for the study of dynamics in the liquid phase. Using this technique, it is possible to obtain information about various relaxation processes in solution, including the motions of molecules in different electronic states, and the transitions between these states. Since the experiment typically measures both electronic relaxation and molecular reorientation, the observed signal can have a complicated form which represents a coupling of these two effects in a way that depends on the particular scheme of decay processes which are present in a given system. We present a general algorithm for deriving the form of the experimental signal for an arbitrary scheme for systems exhibiting these phenomena, assuming that the molecular motion is described by asymmetric rotational diffusion. Several examples are presented and experimental results interpreted using the derived formulas, including cases where (1) the excited state diffusion tenso...