Importance of varying permittivity on the conductivity of polyelectrolyte solutions

Phys Rev Lett. 2015 Sep 11;115(11):118301. doi: 10.1103/PhysRevLett.115.118301. Epub 2015 Sep 10.

Abstract

Dissolved ions can alter the local permittivity of water; nevertheless most theories and simulations ignore this fact. We present a novel algorithm for treating spatial and temporal variations in the permittivity and use it to measure the equivalent conductivity of a salt-free polyelectrolyte solution. Our new approach quantitatively reproduces experimental results unlike simulations with a constant permittivity that even qualitatively fail to describe the data. We can relate this success to a change in the ion distribution close to the polymer due to the buildup of a permittivity gradient.