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A molecular dynamics study of the ionic and molecular permeability of alkanethiol monolayers on the gold electrode surface

  • Nanostructured Systems and Materials
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Abstract

Ionic and molecular permeability of monolayers of alkanethiols on the Au(111) surface in an aqueous NaF solution is investigated using the molecular dynamics (MD) method. The surface charge-driven penetration of the electrolyte components into the monolayer was found to have a threshold. The mechanism of ion permeation comprises two steps, (1) the formation of a polar channel of water molecules which are drawn into the nonpolar monolayer due to local electric field fluctuations (2) transport of ions through the polar channel to the Au(111) surface. It is concluded that the defect-free monolayers are impermeable for the electrolyte components at electrode potentials related to the stability region of the monolayer. The monolayer of hexadecanethiols (—SC16H33) is less permeable with that of hexanethiols (—SC6H13), this is explained in terms of a closer packing structure for longer hydrocarbon tails.

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Authors and Affiliations

  1. Joint Institute for High Temperatures, Russian Academy of Sciences, Izhorskaya ul. 13 (bldg. 2), Moscow, 125412, Russia

    S. A. Kislenko, V. A. Nikitina & R. R. Nazmutdinov

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  1. S. A. Kislenko
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  2. V. A. Nikitina
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  3. R. R. Nazmutdinov
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Correspondence to S. A. Kislenko.

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Original Russian Text © S.A. Kislenko, V.A. Nikitina, R.R. Nazmutdinov, 2015, published in Khimiya Vysokikh Energii, 2015, Vol. 49, No. 5, pp. 382–388.

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Kislenko, S.A., Nikitina, V.A. & Nazmutdinov, R.R. A molecular dynamics study of the ionic and molecular permeability of alkanethiol monolayers on the gold electrode surface. High Energy Chem 49, 341–346 (2015). https://doi.org/10.1134/S0018143915050069

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  • DOI: https://doi.org/10.1134/S0018143915050069

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