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Mapping the ionic fingerprints of molecular monolayers
Joshua Lehr,Justin R. Weeks,Adriano Santos,Gustavo T. Feliciano,Melany I. G. Nicholson,Jason J. Davis,Paulo R. Bueno
Physical Chemistry Chemical Physics Pub Date : 05/12/2017 00:00:00 , DOI:10.1039/C7CP01500C
Abstract

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.

Graphical abstract: Mapping the ionic fingerprints of molecular monolayers
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