Understanding Attenuated Solvent Reorganization Energies near Electrode Interfaces

16 October 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

This manuscript studies the position-dependent profile of Marcus-like outer-sphere reorganization energy near electrode interfaces. We establish the relation between the reorganization energy and the fluctuation in the Madelung potential of redox ions in the electrolyte. The distribution of such potential narrows significantly within the screening length of the electrode, leading to the minimization of electron transfer barrier. In addition, we present a statistical field model that can capture the attenuation of reorganization energy, indicating the generality of this effect near electrode interfaces regardless the molecular details.

Keywords

heterogeneous electron transfer
Madelung potential
outer-sphere reorganization energy
image charge effect

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