Nonlinear conductivity of aqueous electrolytes: Beyond the first Wien effect
Hélène Berthoumieux, Vincent Démery, A. C. Maggs
Abstract
The conductivity of strong electrolytes increases under high electric fields, a nonlinear response known as the first Wien effect. Here, using molecular dynamics simulations, we show that this increase is almost suppressed in moderately concentrated aqueous electrolytes due to the alignment of the water molecules by the electric field. As a consequence of this alignment, the permittivity of water decreases and becomes anisotropic, an effect that can be measured in simulations and reproduced by a model of water molecules as dipoles. We incorporate the resulting anisotropic interactions between the ions into a stochastic density field theory and calculate ionic correlations as well as corrections to the Nernst-Einstein conductivity, which are in qualitative agreement with the numerical simulations.