Electric double layers with surface charge modulations: Novel exact Poisson-Boltzmann solutions

Abstract

Poisson-Boltzmann theory is the cornerstone for soft matter electrostatics. We provide novel exact analytical solutions to this non-linear mean-field approach, for the diffuse layer of ions in the vicinity of a planar or a cylindrical macroion. While previously known solution are for homogeneously charged objects, the cases worked out exhibit a modulated surface charge --or equivalently surface potential-- on the macroion (wall) surface. In addition to asymptotic features at large distances from the wall, attention is paid to the fate of the contact theorem, relating the contact density of ions to the local wall charge density. For salt-free systems (counterions only), we make use of results pertaining to the two-dimensional Liouville equation, supplemented by an inverse approach. When salt is present, we invoke the exact two-soliton solution to the 2D sinh-Gordon equation. This leads to inhomogeneous charge patterns, that are either localized or periodic in space. Without salt, the electrostatic signature of a charge pattern on the macroion fades exponentially with distance for a planar macroion, while it decays as an inverse power-law for a cylindrical macroion. With salt, our study is limited to the planar geometry, and reveals that pattern screening is exponential.

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Cited by in corpus (5)

• Heterogeneous surface charge confining an electrolyte solution
• Electrolytes in regimes of strong confinements: surface charge modulations, osmotic equilibrium and electroneutrality
• Electric double layers with modulated surface charge density: Exact 2D results
• Contact value theorem for electric double layers with modulated surface charge density
• Counterions between walls with surface charge modulations: Exact Poisson-Boltzmann solutions