Semiclassical Assignment of the Vibrational Levels of Molecules with Fermi Resonance: Application to CS2

✍ Scribed by Marc Joyeux

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 223 KB
• Volume: 175
• Category: Article
• ISSN: 0022-2852
• DOI: 10.1006/jmsp.1996.0031

✦ Synopsis

In order to allow unambiguous assignment of the vibrational levels of molecules with Fermi resonance, we suggest replacement of the good quantum number, which is destroyed by the Fermi resonance coupling, by its semiclassical analogue. For this purpose, a rapid and straightforward method for the semiclassical quantization of the experimentalist's Hamiltonian is derived, using the expressions which were obtained recently for similar nondegenerate Hamiltonians with terms not exceeding degree 2. Terms with degree higher than 2, which are unavoidable from the experimentalist's point of view (especially for large energy ranges), are taken into account using a perturbation method. These results are used to reassign fluorescence spectra of CS 2 from 0 to 10 000 cm 01 vibrational energy.