Electrochemical Nonadiabatic Electron Transfer via Tunneling to Solution Species through Thin Insulating Films

Authors

Caleb M. Hill, University of Wyoming
Jiyeon Kim, The University of Texas at AustinFollow
Nataraju Bodappa, The University of Texas at Austin
Allen J. Bard, The University of Texas at Austin

Document Type

Article

Date of Original Version

5-3-2017

Abstract

Described here is a semiquantitative theoretical treatment of the kinetics of outer sphere electrochemical reactions. The framework presented here, which is based on simple physical arguments, predicts heterogeneous rate constants consistent with previous experimental observations (k0 > 10 cm/s). This theory is applied to the analysis of voltammetry experiments involving ultramicroelectrodes modified with thin, insulating oxide films where electronic tunneling between the electrode and redox species in solution (metal-insulator-solution tunneling) is expected to play a prominent role. It is shown that analysis of the voltammetric response of an outer sphere redox couple can be used to track changes in the structure of the adsorbed insulating layer.

Publication Title, e.g., Journal

Journal of the American Chemical Society

Volume

139

Issue

17

Citation/Publisher Attribution

Hill, Caleb M., Jiyeon Kim, Nataraju Bodappa, and Allen J. Bard. "Electrochemical Nonadiabatic Electron Transfer via Tunneling to Solution Species through Thin Insulating Films." Journal of the American Chemical Society 139, 17 (2017): 6114-6119. doi: 10.1021/jacs.6b12104.