Fluorescence polarization as a probe of the rotational dynamics of isolated highly excited molecules
Fluorescence polarization as a probe of the rotational dynamics of isolated highly excited molecules
复制标题
荧光偏振作为孤立高激发分子旋转动力学的探针
DOI：
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发表时间：
1984
期刊：
影响因子：
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通讯作者：
G. McClelland
中科院分区：
文献类型：
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作者：
G. Nathanson;G. McClelland
现在有很多证据表明，孤立的高激发分子的振动模式是强烈混合的，但对这种分子的旋转运动知之甚少。基本的问题是旋转是否近似地与振动分离，或者通过科里奥利力和离心力与振动强烈耦合。为了开发实验方法来回答这个问题，我们提出了电子激发的对称顶部分子进行两种极端类型的旋转运动的荧光偏振计算：规则旋转，其中旋转运动是刚体的旋转运动，以及统计运动，其中，在总角动量和能量守恒的约束下，核能在旋转运动和振动运动之间进行统计分配。这种统计假设产生了一个特定的分布角动量和分子对称轴之间的角度，这反过来又决定了荧光偏振…
There is now much evidence that the vibrational modes of isolated highly excited molecules are strongly mixed, but little is known about the rotational motion of such molecules. The basic question is whether rotation is approximately separable from vibration or is strongly coupled with vibration by Coriolis and centrifugal forces. In an effort to develop experimental methods to answer this question, we present computations of the polarization of fluorescence from electronically excited symmetric top molecules undergoing two extreme types of rotational motion: Regular rotation, for which the rotational motion is that of a rigid body, and statistical motion, in which the nuclear energy is partitioned statistically between rotational and vibrational motion within the constraints of total angular momentum and energy conservation. This statistical assumption yields a particular distribution for the angle between the angular momentum and molecular symmetry axis, which in turn determines the fluorescence polariz...