Intramolecular charge reorganization

The contribution from intramolecular vibrational reorganization, which is small for strong internal bonding, has been neglected. The effective radii for the encounter, a1 and a2, include in addition to the molecular radii of the reactants, a saturated monolayer of solvent around the molecular anion, r is taken as a + a2. Dop, the optical dielectric constant, is equal to the square of the refractive index, and D8 is the static dielectric constant, Ae is the change in charge of the donor, which for our case is -j-1. 

Free coumarin dye is emissive, but complexation of the (7 -cp)Ru moiety to the coumarin chromophore inhibits reorganization of the dye to its polar form in the intramolecular charge transfer (ICT) excited state, thereby resulting in nonemissive complexes in which the MLCT or d-d excited states are lowest in energy. Similarly, the multiple substitution of (ri -cp )Ru on rubrene can also impart new structural, photophysical, and chemical properties to the rubrene molecule. ... 

The charge terms expressed in Cartesian coordinate space are very difBcult to inter] et. Besides, as we shall later see, its elements will carry some contributions frmn the compensatory rotation of polar molecules stipulated by the Edcart-Sayvetz conditions. In the Decius proach, on the other hand, the consideration of diese rotational effects is explicit and, as result, both the effective chaiges and charge fluxes determined are purely intramolecular quantities reflecting the charge reorganization effects acconqiaiiying vibrational distortions. 

The conclusions reached by Costentin and SavOant are in fact quite consistent with our own. The main difference is that, according to these authors, the notion of an imbalanced transition state should be placed within the context of charge localization-delocalization heavy-atom intramolecular reorganization rather than of synchronization (or lack thereof) between charge delocalization and proton transfer. ... 

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