Simulation study of the ferrous ferric electron transfer at a metal--aqueous electrolyte interface

Journal Article · Thu Dec 15 04:00:00 EST 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.467841· OSTI ID:6767962

Smith, B B; Halley, J W ^[1]

---

1. School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

We report a new simulation study of the rate of ferrous--ferric electron transfer at a metal electrolyte interface. In contrast with earlier work, new features in our study include a detailed account of the effects of the field associated with the charging of the electrode, inclusion of entropic effects in the calculated free energy barriers, and a study of the dependence of the relevant free energy surfaces on the distance of the ion from the electrode. The qualitative picture of the reaction mechanism which emerges is significantly more detailed than that in earlier work. The dominant factors in determining the rate and mechanisms of electron transfer are the distance dependence of the work function of the metal, the redox species concentration profile, and the electronic matrix element. Calculated free energy barriers are consistent with experimentally measured ones. We also estimate the equilibrium potential for this reaction from the model, and find it to be consistent with the experimental equilibrium potential.

• DOE Contract Number: FG02-91ER45455
• OSTI ID: 6767962
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 101:12; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
400500 -- Photochemistry
AQUEOUS SOLUTIONS
CHEMICAL REACTIONS
CHEMISTRY
CORROSION
CRACKING
DECOMPOSITION
DISPERSIONS
ELECTROCHEMISTRY
ELECTRODES
ELECTROLYTES
ELECTRON TRANSFER
ELEMENTS
EQUILIBRIUM
INTERFACES
METALS
MIXTURES
PHOTOCHEMISTRY
PYROLYSIS
SIMULATION
SOLUTIONS
STRESS CORROSION
THERMOCHEMICAL PROCESSES