Thermodynamic Causes of the High Diffusion Rate of Atoms in the Superficial Layer of a Metallic Electrode
Yu. Ya. Andreev
Moscow State Institute of Steel and Alloys, Leninskii pr. 2, Moscow, Russia
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Received January 31, 2006
Abstract — Concentration of vacancies NV(S) in a superficial layer (SL) of fcc lattices of Ag, Cu, and Au metals is thermodynamically estimated and analyzed. The calculations are based on a thermodynamic vacancy model of the metal SLs, by which the NV(S) value is related to the surface Gibbs energy 
Gs = 
RT ln NV(S). A strongGs dependence on the electrode potential and the zero point value of the metal results in the increase in NV(S) value, which reaches nearly 10
2 at standard potentials of the above metals. The high surface self-diffusivity of atoms (D
10
15 cm2/s) calculated from the in situ STM measurements of the electrode surfaces is due to the high concentration of vacancies in the metal SLs.
Gs = RT ln NV(S). A strongGs dependence on the electrode potential and the zero point value of the metal results in the increase in NV(S) value, which reaches nearly 102 at standard potentials of the above metals. The high surface self-diffusivity of atoms (D1015 cm2/s) calculated from the in situ STM measurements of the electrode surfaces is due to the high concentration of vacancies in the metal SLs.
PACS numbers: 05.70.Np; 68.35.Md
DOI: 10.1134/S003317320701002X