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

E-mail: YuAndr@rambler.ru

Received January 31, 2006

Abstract—Concentration of vacancies N_V(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 N_V(S) value is related to the surface Gibbs energy G_s = RT ln N_V(S). A strong
G_s dependence on the electrode potential and the zero point value of the metal results in the increase in N_V(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

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