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Nonequilibrium Thermodynamics Formalism for Marcus Theory of Heterogeneous and Self-Exchange Electron-Transfer Rate Constants

Richa Sethi and M. V. Sangaranarayanan*

Department of Chemistry, Indian Institute of Technology-Madras Chennai-600036 India

J. Phys. Chem. A, 2008, 112 (18), pp 4308–4313

DOI: 10.1021/jp800473k

Publication Date (Web): March 28, 2008

Corresponding author. E-mail: sangara@iitm. ac.in.

Abstract

The cross-exchange electron-transfer rate constant expression of Marcus is derived from the Flux−force formalism of non-equilibrium thermodynamics. The relationship governing the Onsager's phenomenological coefficients for cross-exchange and self-exchange electron-transfer processes is deduced. Onsager's phenomenological coefficient pertaining to the Butler−Volmer equation is derived and estimated from the experimental exchange current densities. The correlation between the heterogeneous and the homogeneous electron-transfer rate constants derived by Marcus is analyzed in terms of the corresponding phenomenological coefficients.

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