Exploring Bridges between Quantum Transport and Electrochemistry. II. A Theoretical Study of Redox-Active Monolayers

Abstract

An electrochemical charge transfer model derived from quantum transport methods is extended to capture ultrafast linear sweep voltammetry. It is applied to a model electrochemical tunneling system consisting of a passivating monolayer terminated by redox-active groups. On the basis of Gerischer’s density of states formulation, electronic coupling independent voltammetric spectra are predicted from which the redox reorganization energy may be extracted. Moreover, two methods, based on voltammetric peak potentials and the degree of reaction completion are examined as possible techniques to measure the electronic coupling between redox species and a substrate. In general, this work aims to further the translation of quantum transport derived electrochemical concepts into directly measurable electrochemical properties.