Interparticle Interactions in Nonlocal Media: Attraction and Repulsion from Charge-Polarization Coupling

TL;DR

This paper introduces a nonlocal dielectric model that accounts for solvent structuring and polarization correlations, revealing complex interparticle interactions like attraction between like-charged particles and long-range forces.

Contribution

It develops a nonlocal dielectric theory that incorporates spatial polarization correlations, explaining phenomena unexplained by classical models.

Findings

Like-charged surfaces can attract at long range.

Oppositely charged objects can repel.

Neutral matter can exhibit effective electrical mobility.

Abstract

Recent measurements of microsphere interactions in diverse media suggest that the standard dielectric-continuum models of solution-phase interactions are fundamentally incomplete. Experiments indicate that the interactions of charged particles in liquids can be dominated by solvent structuring at interfaces, thereby motivating the concept of electrosolvation. While interfacial spectroscopy and molecular simulations have established that solvent molecules can exhibit net orientation at interfaces, conventional theoretical frameworks treat the fluid as a structureless medium described by a constant dielectric permittivity. This view does not envisage a contribution of interfacial polarization to interactions at longer range. Here, we employ nonlocal dielectric theory accounting for spatial correlations in polarization to describe interactions in solution. This model permits both charge and polarization to govern interactions, leading to dramatic departures from classical expectations. Specifically, the balance between charge and polarization generates a framework of symmetric (repulsive) and antisymmetric (attractive) interactions, wherein: (i) like-charged surfaces can attract at long range, (ii) oppositely charged objects can repel, and (iii) neutral matter can acquire effective electrical mobility and display long-range forces-potentially explaining long-range hydrophobic attraction. Further, like-charged biomolecules can attract in aqueous electrolytes even for modest polarization correlation lengths ($\xi=2$ \AA). Our results also suggest that electrosolvation effects may underpin flocculation in suspended matter, which has traditionally been attributed to attractive dispersion forces. These findings indicate how solvent structuring and correlations may play a dominant, complex role in fluid-phase physics.