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Polar liquids at charged interfaces: A dipolar shell theory

Author(s)
de Souza, J Pedro; Kornyshev, Alexei A; Bazant, Martin Z
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Abstract
<jats:p> 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 decaying spatial 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. </jats:p>
Date issued
2022-06-28
URI
https://hdl.handle.net/1721.1/145497
Department
Massachusetts Institute of Technology. Department of Chemical Engineering; Massachusetts Institute of Technology. Department of Mathematics
Journal
The Journal of Chemical Physics
Publisher
AIP Publishing
Citation
de Souza, J Pedro, Kornyshev, Alexei A and Bazant, Martin Z. 2022. "Polar liquids at charged interfaces: A dipolar shell theory." The Journal of Chemical Physics, 156 (24).
Version: Final published version

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