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The electronic coupling between the two multielectronic states is described by an additional term β, not indicated in eq 4. For the purposes of this discussion, we have assumed that this term is constant.
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49
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The homogeneous broadening of the individual vibronic transitions characteristic of these complexes in fluid solution at room temperature suggests that low-frequency modes (including the solvent) can be treated classically in the limit ℏω ≪ kT. This approximation allows for a reduction in the number of fitting parameters and allows each vibronic component to be described by a Gaussian distribution function.
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50
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1842289665
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Low-temperature emission spectra in this class of molecules have similar features, implying that there are no dramatic differences in the nature of the vibrational modes that couple to excited-state relaxation.
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It should be noted that this calculation effectively describes the energy separation between the ground state and the Franck-Condon state. Factors such as spin-orbit coupling and outer-sphere reorganization are therefore not accounted for.
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It should be noted that such a torsional mode would be expected to occur at very low frequency and would be difficult to observe. This mode must become active at some stage to reformulate the canted ground state, but it is unclear whether it plays a role as an acceptor in the relaxation mechanism.
-
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