Document Type
Article
Department/Program
Physics
Journal Title
Journal of Chemical Physics
Pub Date
1997
Publisher
American Institute of Physics
Volume
107
Issue
14
First Page
5460
Abstract
An intuitive picture of Λ-doubling in diatomic molecules is presented using a semiclassical theory. A common view of Λ-doubling as arising from electrons “lagging” behind the rotating internuclear axis is shown to be misleading; rather, the eigenfunctions are symmetric about the molecular axes and can be expressed as a superposition of pure nonrotating orbitals and travelling waves. These results are shown to be consistent with a full quantum treatment. We also examine, for the first time, time-dependent states, by monitoring expectation values of electronic- and nuclear-angular momenta. For low rotation frequency, the expectation value of the electronic-angular momentum locks onto the rotating internuclear axis, while for high rotation frequency it locks onto the space-fixed total-angular momentum axis. At intermediate frequencies is a complicated behavior.
Recommended Citation
Kovalenko, Laurie J. and Delos, John B., Semiclassical Model of Λ-doublet States in Diatomic Molecules (1997). Journal of Chemical Physics, 107(14), 5460-5472.
https://doi.org/10.1063/1.474251
DOI
https://doi.org/10.1063/1.474251
