Mapping the ionic fingerprints of molecular monolayers

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2017-01-01

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Lehr, Joshua
Weeks, Justin R.
Santos, Adriano [UNESP]
Feliciano, Gustavo T. [UNESP]
Nicholson, Melany I. G. [UNESP]
Davis, Jason J.
Bueno, Paulo R. [UNESP]

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We have previously proposed, and experimentally resolved, an ionic charge relaxation model for redox inactive self-assembled monolayers (SAMs) on metallic electrodes in contact with a liquid electrolyte. Here we analyse, by capacitance spectroscopy, the resistance and capacitance terms presented by a range of thiolated molecular films. Molecular dynamics simulations support a SAM-specific energy barrier to solution-phase ions. Once surmounted, the entrapped ions support a film embedded ionic capacitance and non-faradaic relaxation, which can be assigned as a particular case of general electrochemical capacitance.

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Physical Chemistry Chemical Physics, v. 19, n. 23, p. 15098-15109, 2017.