ANOMALOUS ROTATIONAL LINE INTENSITIES IN ELECTRONIC TRANSITIONS OF POLYATOMIC MOLECULES: AXIS-SWITCHING
ANOMALOUS ROTATIONAL LINE INTENSITIES IN ELECTRONIC TRANSITIONS OF POLYATOMIC MOLECULES: AXIS-SWITCHING
复制标题
多原子分子电子跃迁中的反常旋转线强度：轴转换
DOI：
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发表时间：
1965
期刊：
影响因子：
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通讯作者：
J. Watson
中科院分区：
文献类型：
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作者：
J. T. Hougen;J. Watson
在对振动和旋转的分子进行计算时，定义一个以某种方式固定在分子上的轴系是很方便的。然而，通常的分子固定轴系的取向不仅取决于原子核的瞬时位置，而且还取决于原子核被认为偏离的平衡位置。因此，当一个足够低对称性的分子经历伴随着几何变化的电子跃迁时，一般来说，有必要考虑两个分子固定轴系统，对应于两个不同的电子状态。轴系统从一种电子状态到另一种电子状态的这种变化将被称为轴切换。这两个坐标系可以通过3 × 3旋转矩阵联系起来，使它们重合。 这个矩阵的元素是两个电子态的平衡几何形状以及分子中原子的瞬时位置的函数。轴切换开关
It is convenient when performing calculations on a vibrating and rotating molecule to define an axis system which is somehow fixed to the molecule. The orientation of the usual molecule-fixed axis system, however, depends not only upon the instantaneous positions of the nuclei, but also upon the equilibrium positions from which the nuclei are regarded as being displaced. Thus, when a molecule of low enough symmetry undergoes an electronic transition accompanied by a change in geometry, it will, in general, be necessary to consider two molecule-fixed axis systems, corresponding to the two different electronic states. This change in axis system from one electronic state to another will be called axis-switching. The two axis systems can be related to each other by the 3 × 3 rotation matrix which brings them into coincidence. The elements of this matrix are functions of the equilibrium geometries of the two electronic states as well as of the instantaneous positions of the atoms in the molecule. Axis-switchin...