Abstract
Diffusion-controlled fluorescence quenching for perylene by dinitrobenzene has been examined; Smoluchowski's equation does not apply. The reaction radius R in relatively viscous solvents (isopropanol and benzonitrile) exceed the contact radius by more than a factor two. R decreases as the mutual diffusion coefficient D increases. The in D dependence for R has been used to determine the electron-tunneling parameters. The Frank-Condon factors increase with the electron-acceptor strength. Electron-tunneling barrier heights from excited perylene to the oxidizing agent have been calculated. It is concluded that virtual solvent states are involved.
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