The wave functions of electronically degenerate states
The wave functions of electronically degenerate states
复制标题
电子简并态的波函数
DOI：
10.1080/00268976100100581
复制
发表时间：
1961
期刊：
影响因子：
--
通讯作者：
A. McLachlan
中科院分区：
文献类型：
--
作者：
A. McLachlan
简并电子态中的核与电子运动的动力学耦合由一个复杂的振动波方程来描述，因为绝热电子函数在振动过程中迅速变化。霍贝和麦克拉克伦试图证明如何找到电子波函数的特殊线性组合，这些组合变化缓慢，并导致更简单的波动方程。本文指出了他们论证中的一个错误，并加以纠正，说明简单波动方程仍然是成立的。新方法类似于简并微扰理论中的货车Vleck变换，也适用于几乎简并的分子。
The dynamical coupling of nuclear and electronic motions in a degenerate electronic state is described by a complicated vibronic wave equation, because the adiabatic electronic functions vary rapidly during the vibrations. Hobey and McLachlan tried to show how special linear combinations of the electronic wave functions could be found, which vary slowly, and lead to a simpler wave equation. This paper points out a mistake in their argument, but corrects it, and shows that the simple wave equation is still justified. The new method is similar to Van Vleck's transformation in degenerate perturbation theory, and also applies to molecules which are almost degenerate.