15min:

F. PÉREZ-BERNAL, Departamento de Física Aplicada, Facultad de Ciencias Experimentales, Avda. de las FF.AA. s/n, Universidad de Huelva, 21071 Huelva, Spain; F. IACHELLO AND P. H. VACCARO, Departments of Physics and Chemistry, Yale University, New Haven, CT 06520 USA; H. ISHIKAWA, H. TOYOSAKI AND N. MIKAMI, Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578 Japan.

Emission spectra obtained from bulk-gas methinophosphide (HCP) have been interpreted through use of a novel algebraic scheme that explicitly takes into account inherent non-rigidity of the molecular framework. Fluorescence accompanying selective excitation of individual ¹A'' - ^{1 +} vibronic bands was dispersed under moderate resolution, with the appearance of substantial activity in the ₂ bending mode reflecting the bent-from-linear nature of the transition. Aside from providing an economical parameterization for observed patterns of vibrational term energies, the algebraic approach affords a robust and facile means for the quantitative evaluation of multidimensional Franck-Condon factors. These results, as well as subsequent extensions designed to account for non-Condon effects, will be discussed in order to further elucidate the unique structure and dynamics exhibited by participating electronic states.