Mapping the ionic fingerprints of molecular monolayers
Literature Information
Joshua Lehr, Justin R. Weeks, Adriano Santos, Gustavo T. Feliciano, Melany I. G. Nicholson, Jason J. Davis, Paulo R. Bueno
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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