Visualization of rigorous sum rules for Franck-Condon factors: spectroscopic applications to Xe 2

• Autores: M. Selg
• Localización: Journal of molecular spectroscopy, ISSN 0022-2852, Vol. 220, Nº 2, 2003, págs. 187-200
• Idioma: inglés
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• Resumen

  • A fully quantum mechanical approach to the calculation and normalization of the Franck–Condon factors for diatomic species is described. The treatment is based on the fundamental demand of completeness of the energy eigenfunctions, which results in the rigorous sum rule for the Franck–Condon overlap integrals. The importance of this general rule has been discussed and thoroughly illustrated in the case of diatomic xenon molecules. Exactly solvable reference potentials for this system have been constructed and a complete basis of the actual energy eigenstates (including both bound and scattering states) has been created. Several direct spectroscopic applications to xenon excimers are presented, and their good agreement with relevant experimental data demonstrated. In particular, a kinetic model is proposed to explain the observed oscillatory structures in the fluorescence spectra of Xe2∗ [Chem. Phys. Lett. 117 (1985) 301] related to their classical left turning points. The same model gives a uniform explanation to the well-known first and second emission continua of rare gases.