The influence of charged-induced variations in the local permittivity on the static and dynamic properties of polyelectrolyte solutions

Abstract

There is a large body of literature investigating the static and dynamic properties of polyelectrolytes due both to their widespread application in industrial processes and their ubiquitous presence in biology. Because of their highly charged nature, polyelectrolytes tend to alter the local dielectric permittivity of the solution within a few nanometers of their backbone. This effect has, however, been almost entirely ignored in both simulations and theoretical work. In this article we apply our recently developed electrostatic solver based on Maxwell's equations to examine the effects of the permittivity reduction in the vicinity of the polyelectrolyte. We first verify our new approach by calculating and comparing ion distributions around a linear fixed polyelectrolyte and find both quantitative and qualitative changes in the ion distribution. Further simulations with an applied electric field show that the reduction in the local dielectric constant increases the mobility of the chains by approximately ten percent. More importantly, variations in the local dielectric constant lead to qualitatively different behavior of the conductivity.

References in corpus (4)

• Importance of hydrodynamic shielding for the dynamic behavior of short polyelectrolyte chains
• Importance of Varying Permittivity on the Conductivity of Polyelectrolyte Solutions
• Self-consistent field model for strong electrostatic correlations and inhomogeneous dielectric media
• On the importance of hydrodynamic interactions in polyelectrolyte electrophoresis

Cited by in corpus (2)

• Dissipative Particle Dynamics for Systems with Polar Species
• The explicit characterization of counterion dynamics around a flexible polyelectrolyte