Adiabaticity of electron transfer at an electrode

Journal Article · Thu Feb 12 04:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100288a023· OSTI ID:7042251

Morgan, J D; Wolynes, P G

A simple description of the kinetics of electron transfer at an electrode is developed which includes the effects of both outer-sphere solvent dielectric relaxation and electron tunneling. From this description, an adiabaticity criterion is obtained which determines when the rate of the electron transfer is adiabatic, that is, determined by solvent relaxation dynamics, or diabatic, determined by electron tunneling dynamics. Rate constants are also obtained for the diabatic and adiabatic limiting cases and the intermediate regime in which the dynamics of both processes are important. The degree of localization of the electron transfer and the dependence of the rate on the electrode potential, the Miller indices of the electrode surface, the surface site of the reacting ion, and the distance of the ion from the electrode are examined. Possible extensions of the formalism to include other important factors are also discussed.

• Research Organization: Univ. of Illinois, Urbana
• OSTI ID: 7042251
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:4; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
ADIABATIC PROCESSES
CHEMICAL REACTION KINETICS
DATA
ELECTRODES
ELECTRON TRANSFER
INFORMATION
KINETICS
NUMERICAL DATA
POTENTIALS
REACTION KINETICS
SOLVENTS
SURFACES
THEORETICAL DATA