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X-rayreflectivity studies demonstrate the condensation of a monovalent ion at the electrified interface between electrolyte solutions of water and 1,2-dichloroethane. Predictions of the ion distributions by standard Poisson–Boltzmann (Gouy–Chapman) theory are inconsistent with these data at higher applied interfacial electric potentials. Calculations from a Poisson–Boltzmann equation that incorporates a nonmonotonic ion-specific potential of mean force are in good agreement with the data.


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