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There is a large body of literature investigating the static and dynamicproperties of polyelectrolytes due both to their widespread application inindustrial processes and their ubiquitous presence in biology. Because of theirhighly charged nature, polyelectrolytes tend to alter the local dielectricpermittivity of the solution within a few nanometers of their backbone. Thiseffect has, however, been almost entirely ignored in both simulations andtheoretical work. In this article we apply our recently developed electrostaticsolver based on Maxwell's equations to examine the effects of the permittivityreduction in the vicinity of the polyelectrolyte. We first verify our newapproach by calculating and comparing ion distributions around a linear fixedpolyelectrolyte and find both quantitative and qualitative changes in the iondistribution. Further simulations with an applied electric field show that thereduction in the local dielectric constant increases the mobility of the chainsby approximately ten percent. More importantly, variations in the localdielectric constant lead to qualitatively different behavior of theconductivity.

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