Image charge effects under metal and dieletric boundary conditions

Abstract

Image charge effect is a fundamental problem in electrostatics. However, a proper treatment at the continuum level for many-ion systems, such as electrolyte solutions or ionic liquids, remains an open theoretical question. Here, we demonstrate and systematically compare the image charge effects under metal and dielectric boundary conditions (BCs), based on a renormalized Gaussian-fluctuation theory. Our calculations for a simple 1:1 symmetric electrolyte in the point-charge approximation show that the double-layer structure, capacitance, and interaction forces between like-charged plates depend strongly on the types of boundaries, even in the weak-coupling regime. Like-charge attraction is predicted for both metal and dielectric BCs. Finally, we comment on the effects of a dielectrically-saturated solvent layer on the metal surface. We provide these results to serve as a baseline for comparison with more realistic molecular dynamics simulations and experiments.

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Cited by in corpus (3)

• Brownian dynamics simulations of electric double-layer capacitors with tunable metallicity
• Unified microscopic theory of equilibrium thermodynamics and ion association in aqueous and non-aqueous electrolytes with explicit hard-core size
• Classical theory of electron-ion correlations at electrochemical interfaces: Closing the circuit from double-layer charging to ion adsorption