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Article
Semiclassical Model of Λ-doublet States in Diatomic Molecules
Journal of Chemical Physics
  • Laurie J. Kovalenko
  • John B. Delos, William & Mary
Document Type
Article
Department/Program
Physics
Pub Date
1-1-1997
Publisher
American Institute of Physics
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.

DOI
https://doi.org/10.1063/1.474251
Disciplines
Citation Information
Laurie J. Kovalenko and John B. Delos. "Semiclassical Model of Λ-doublet States in Diatomic Molecules" Journal of Chemical Physics Vol. 107 Iss. 14 (1997) p. 5460 - 5472
Available at: http://works.bepress.com/john-delos/88/