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Phys. Rev. E 73, 021606 (2006) [12 pages]

Excess nonspecific Coulomb ion adsorption at the metal electrode/electrolyte solution interface: Role of the surface layer

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A. M. Gabovich, Yu. A. Reznikov, and A. I. Voitenko
Institute of Physics, National Academy of Sciences of Ukraine, 46 Nauka Ave., Kyiv 03028, Ukraine

Received 5 October 2005; revised 5 January 2006; published 27 February 2006

Excession adsorption Gamma induced by the polarization image forces inthe system of a metal electrode/symmetric electrolyte solution separated byan insulating interlayer has been calculated. The adopted theoretical schemeinvolves the Coulomb Green's function in a three-layer system withsharp interfaces and specular reflection at them. The influence ofthe spatial dispersion of the dielectric permittivities epsilon _i(k) in allthe three media on the image force energy W_im andthe adsorption Gamma has been analyzed, where k is thewave vector. A comparison with the classical model, where epsilon _i=const,has been carried out. It has been shown that boththe Debye-Hückel ion screening and the spatial dispersion of thesolvent contribution epsilon _solv(k) to the overall dielectric function epsilon _el(k) ofthe electrolyte solution lead to the qualitative difference with theresults for the classical model. In particular, in a widerange of ion concentrations n₀ a thin interlayer L5–10 Å effectivelyscreens out the attractive influence of the metallic electrode, sothat the net Coulomb adsorption may become repulsive. The approachand the results obtained qualitatively describe two physically different situations.Specifically, the introduced interlayer corresponds either to the dense near-electrode(inner) electrolyte layer or to the intentionally deposited control coatingof arbitrary thickness.

©2006 The American Physical Society

URL:	http://link.aps.org/doi/10.1103/PhysRevE.73.021606
DOI:	10.1103/PhysRevE.73.021606
PACS:	68.03.-g; 77.22.Ch; 82.45.Un; 68.43.-h 68.03.-g Gas-liquid and vacuum-liquid interfaces 77.22.Ch Permittivity (dielectric function) 82.45.Un Dielectric materials in electrochemistry 68.43.-h Chemisorption/physisorption: adsorbates on surfaces YEAR: 2006
KEYWORDS:	adsorption, interface phenomena, electrodes, electrolytes, permittivity, dielectric function

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