Electronic friction and electron transfer rates at metallic electrodes

A theory is presented for the rate constant k for electron transfer between a metal electrode and a redox couple solute in solution, in or near the electronically adiabatic regime. The departure of k from its electronically adiabatic transition state theory limit kTST is described via Grote–Hynes th...

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Bibliographic Details
Published in:The Journal of chemical physics 1993-11, Vol.99 (9), p.6517-6530
Main Authors: SMITH, B. B, HYNES, J. T
Format: Article
Language:English
Subjects:
400400 - Electrochemistry
ADIABATIC APPROXIMATION
Chemical thermodynamics
CHEMISTRY
DISPERSIONS
ELECTROCHEMISTRY
ELECTRODES
ELECTRON TRANSFER
ELECTRON-HOLE DROPLETS
ELEMENTS
Exact sciences and technology
General and physical chemistry
General. Theory
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
METALS
MIXTURES
PLASMA
REDOX POTENTIAL
SOLID-STATE PLASMA
SOLUTES
SOLUTIONS
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Summary:A theory is presented for the rate constant k for electron transfer between a metal electrode and a redox couple solute in solution, in or near the electronically adiabatic regime. The departure of k from its electronically adiabatic transition state theory limit kTST is described via Grote–Hynes theory, and includes two sources of friction. The electronic friction arises from excitation of electron hole pairs in the metal, i.e., electronic nonadiabaticity effects. The solvent friction arises from solvent dynamical effects. Both features can result in significant reduction of k below kTST, and their interplay can lead to interesting nonmonotonic variations with reaction overpotential.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.465843