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Perhaps this band results from a transition with a different direction of polarization. Another interpretation might be in terms of Franck - Condon transitions that arise from higher vibrational states that are lower than the potential energy maximum. In that case, the two-state model underlying Equation (1) would be an oversimplification, which cannot be avoided on the basis of the available spectra, however. See M. Dohle, J. Manz, G. K. Paramonov, Ber. Bunsen-Ges. Phys. Chem. 1995, 99, 478-484.
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