Abstract
AbstractModel calculations are reported aimed at interpreting the Raman excitation profiles observed by Lichtmann et al. They refine earlier calculations by Siebrand and Zgierski based on displaced harmonic oscillators. A distribution of conjugation lengths is introduced and the dependence of the model parameters, in particular the resonant state energy, on this length is investigated. This, together with an allowance for vibrational frequency changes and non‐Condon effects, yields a much improved fit to the observed profiles. The results suggest a narrow distribution of relatively short conjugation lengths (⩽20 double bonds), contrary to most earlier reported distributions based on the dispersion of Raman bands, but comparable to a distribution based on isomerization kinetics.
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