Abstract
Emission spectra obtained from bulk-gas methinophosphide (HCP) have been interpreted by means of a Lie algebraic theory that describes explicit non-rigidity of the molecular framework. Fluorescence accompanying selective excitation of A ̃ 1 A″– X ̃ 1Σ + vibronic bands was dispersed under moderate resolution, with substantial activity of the ν 2 H–C–P bending mode reflecting the bent-from-linear nature of the A ̃ ← X ̃ transition. Aside from furnishing an economical parameterization for energy level patterns, the algebraic treatment permits Franck–Condon intensities to be evaluated quantitatively. The equilibrium structure deduced for the A ̃ 1 A″ state is in good accord with quantum chemistry calculations except for substantially less than predicted elongation of the C–P bond upon electron promotion.
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