4.8 Article

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces

Journal

PHYSICAL REVIEW LETTERS
Volume 115, Issue 25, Pages -

Publisher

AMER PHYSICAL SOC
DOI: 10.1103/PhysRevLett.115.256102

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A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

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