Electrostatic Correlation Augmented Self-Consistent Field Theory and Its Application to Polyelectrolyte Brushes

Abstract

Modeling ion correlations in inhomogeneous polymers and soft matters with spatially varying ionic strength or dielectric permittivity remains a great challenge. Here, we develop a new theory which systematically incorporates electrostatic fluctuations into the self-consistent field theory for polymers. Applied to polyelectrolyte brushes, the theory predicts that ion correlations induce non-monotonic change of the brush height: collapse followed by reexpansion. The scaling analysis elucidates the competition between the repulsive osmotic pressure due to translational entropy and the attraction induced by ion correlations. We also clarify the absence of causal relationship between the brush collapse-reexpansion and the inversion of the surface electrostatic potential. Furthermore, strong ion correlations can trigger microphase separation, either in the lateral direction as pinned micelles or in the normal direction as oscillatory layers. Our theoretical predictions are in good agreement with the experimental results reported in the literature.

References in corpus (16)

• Direct observation of charge inversion by multivalent ions as a universal electrostatic phenomenon
• Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes
• Theory of competitive counterion adsorption on flexible polyelectrolytes : Divalent salts
• Electrostatic Correlations and the Polyelectrolyte Self Energy
• Weak and Strong Coupling Theories for Polarizable Colloids and Nano-Particles
• Understanding the Salt Effects on the Liquid-Liquid Phase Separation of Proteins
• Polyelectrolyte-Compression Forces between Spherical DNA Brushes
• On the theoretical description of weakly charged surfaces
• Electrostatic correlation induced ion condensation and charge inversion in multivalent electrolytes
• Rod-like Polyelectrolyte Brushes with Mono- and Multivalent Counterions
• On the nature of overcharging and charge inversion in electrical double layers
• Self-Consistent Description of Vapor-Liquid Interface in Ionic Fluids
• Ion correlation driven like-charge attraction in multivalent salt solutions
• Distribution of counterions and interaction between two similarly charged dielectric slabs: Roles of charge discreteness and dielectric inhomogeneity
• Effects of Ionic Strength on the Morphology, Scattering, and Mechanical Response of Neurofilament-Derived Protein Brushes
• Ion Correlation-Driven Hysteretic Adhesion and Repulsion between Opposing Polyelectrolyte Brushes