Polar Liquids at Charged Interfaces: A Dipolar Shell Theory

Abstract

The structure of polar liquids and electrolytic solutions, such as water and aqueous electrolytes, at interfaces underlies numerous phenomena in physics, chemistry, biology, and engineering. In this work, we develop a continuum theory that captures the essential features of dielectric screening by polar liquids at charged interfaces, including oscillations in charge and mass, starting from the molecular properties of the solvent. The theory predicts an anisotropic dielectric tensor of interfacial polar liquids previously studied in molecular dynamics simulations. We explore the effect of the interfacial polar liquid properties on the capacitance of the electrode/electrolyte interface and on hydration forces between two plane-parallel polarized surfaces. In the linear response approximation, we obtain simple formulas for the characteristic decay lengths of molecular and ionic profiles at the interface.

References in corpus (5)

• Interfacial layering in the electric double layer of ionic liquids
• Primitive Model Electrolytes in the Near and Far Field: Decay Lengths from DFT and Simulations
• The nonlocal dielectric response of water in nanoconfinement
• Structural interactions in ionic liquids linked to higher order Poisson-Boltzmann equations
• The double-layer structure of overscreened surfaces by smeared-out ions