Macroscopic charge segregation in driven polyelectrolyte solutions

Abstract

Understanding the behavior of charged complex fluids is crucial for a plethora of important industrial, technological, and medical applications. Here, using coarse-grained molecular dynamics simulations, we investigate the properties of a polyelectrolyte solution with explicit counterions and implicit solvent that is driven by a steady electric field. By properly tuning the interplay between interparticle electrostatics and the applied electric field, we uncover two non-equilibrium continuous phase transitions as a function of the driving field. The first transition occurs from a homogeneous mixed phase to a macroscopic charge-segregated phase in which the polyelectrolyte solution self-organizes to form two lanes of like-charges, parallel to the applied field. We show that the fundamental underlying factor responsible for the emergence of this charge segregation in the presence of an electric field is the excluded volume interactions of the drifting polyelectrolyte chains. As the driving field is increased further, a re-entrant transition is observed from a charge-segregated phase to a homogeneous phase. The re-entrance is signaled by a decrease in the mobility of the monomers and counterions as the electric field is increased. Furthermore, with multivalent counterions, a counterintuitive regime of negative differential mobility is observed in which the charges move progressively more slowly as the driving field is increased. We show that all these features can be consistently explained using an intuitive trapping mechanism that operates between the oppositely moving charges, and present numerical evidence to support our claims. Parameter dependencies and phase diagrams are studied to better understand charge segregation in such driven polyelectrolyte solutions.