A Model Electron Transfer Reaction in Confined Aqueous Solution - Sorbonne Université
Article Dans Une Revue ChemPhysChem Année : 2021

A Model Electron Transfer Reaction in Confined Aqueous Solution

Résumé

Liquid water confined within nanometer-sized channels exhibits a strongly reduced local dielectric constant perpendicularly to the wall, especially at the interface, and this has been suggested to induce faster electron transfer kinetics at the interface than in the bulk. We study a model electron transfer reaction in aqueous solution confined between graphene sheets with classical molecular dynamics. We show that the solvent reorganization energy is reduced at the interface compared to the bulk, which explains the larger rate constant. However, this facilitated solvent reorganization is due to the partial desolvation by the graphene sheet of the ions involved in the electron transfer and not to a local dielectric constant reduction effect.
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Dates et versions

hal-03369284 , version 1 (07-10-2021)

Identifiants

Citer

Jean-François Olivieri, Damien Laage, James T. Hynes. A Model Electron Transfer Reaction in Confined Aqueous Solution. ChemPhysChem, 2021, In Memoriam: Prof. Jean-Michel Savéant, 22 (21), pp.2247-255. ⟨10.1002/cphc.202100351⟩. ⟨hal-03369284⟩
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