Unusual Variation of Franck-Condon Factors for the O_{2} Schumann-Runge Band System.

Abstract

Morse oscillator wave functions have been used to calculate an extensive array of Franck-Condon ictors for the O3 Schumaun-Runge (B3 %7 - X j) band system. Unlike all previously reported "ranek-Condon factors, these results are qualitatively different from those expected on the basis of the lassical Franck-Condon principle, in the occurrence of a primary intensity maximum that derives from he dependence of maximum wave function amplitude on potential well width, rather than on maximum rozimity of classical turning points. This dependence arises for transitions that involve vibrational levels ear the dissocation limit, and that occur between electronic states with greatly different equilibrium aternuclear separations.