Continuous Self Energy of Ions at the Dielectric Interface

Abstract

We present a simple, unified theory for the self-energy of an ion near a dielectric interface. Our theory accounts for both the short-range (solvation) and long-range (image force) electrostatic forces, charge polarization induced by these forces, and the cavity energy. In contrast to previous models, our self energy is continuous across the interface and thus applicable to both the water and air (oil) sides of the interface. With no fitting parameters, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

5 pages, 4 figures

References in corpus (5)

• Ions at the air-water interface: An end to one hundred year old mystery?
• Surface tensions, surface potentials and the Hofmeister series of electrolyte solutions
• Surface tension of electrolytes: Hydrophilic and hydrophobic ions near an interface
• Surface and interfacial tensions of Hofmeister electrolytes
• Monovalent Ion Condensation at the Electrified Liquid/Liquid Interface

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• A Brief Review of Continuous Models for Ionic Solutions: the Poisson-Boltzmann and Related Theories
• Image charge effects under metal and dieletric boundary conditions
• Poisson-Boltzmann theory with non-linear ion correlations
• Ion Correlation-Driven Hysteretic Adhesion and Repulsion between Opposing Polyelectrolyte Brushes