Abstract
The intermolecular electron transfer reaction between a biphenyl anion and pyrene in supercritical ethane was studied using pulse radiolysis. Second-order electron transfer rates were found to be of the order of 10 11 M −1 s −1. The rate constants appear to be approximately constant over the pressure range 55–133 bar and slower than the predicted diffusion-controlled rate constants. Two possibilities are discussed that could explain the present results: diffusion constants that are not well predicted by the hydrodynamic equation; or a solvent reorganization energy of approximately 0.35 eV and dependent on pressure. The reorganization energy E r of non-polar supercritical ethane was estimated from the observed rate constant using the modified Marcus equation. E r may be larger than normally expected for non-polar solvents because of density fluctuations.
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