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Nonequilibrium thermodynamics formalism for Marcus theory of heterogeneous and self-exchange electron-transfer rate constants.

Sethi R, Sangaranarayanan MV

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

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.

Published 2 May 2008 in J Phys Chem A, 112(18): 4308-13.
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