A Critical Assessment of Classical and Semi-Classical Models for Electron Transfer Reactions in Solution

Charge-recombination rates in contact radical-ion pairs, formed between aromatic hydrocarbons and nitriles in supercritical CO(2) and heptane, decrease with the exothermicity of the reactions until they reach -70 kcal mol(-1), but from there on an increase is observed. The first decrease in rate is typical of the "inverted region" of electron-transfer reactions. The change to an increase in the rate for ultra-exothermic electron transfer indicates a new free-energy relationship. We show that the resulting "double-inverted region" is not due to a change in mechanism. It is an intrinsic property of electron-transfer reactions, and it is due to the increase of the reorganisation energy with the reaction exothermicity.

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A Critical Assessment of Classical and Semi-Classical Models for Electron Transfer Reactions in Solution

Cited by 61 publications

References 235 publications

Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross‐Rate Theory

Intermolecular Electron Transfer Reactivity for Organic Compounds Studied Using Marcus Cross‐Rate Theory

Redox Modulation by Molecular Recognition

Electron Transfer in Supercritical Carbon Dioxide: Ultraexothermic Charge Recombination at the End of the “Inverted Region”

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