Role of Viscosity in Deviations from the Nernst–Einstein Relation

Deviations from the Nernst–Einstein relation are commonly attributed to ion–ion correlation and ion pairing. Despite the fact that these deviations can be quantified by either experimental measurements or molecular dynamics simulations, there is no rule of thumb to tell the extent of deviations. Here, we show that deviations from the Nernst–Einstein relation are proportional to the inverse viscosity by exploring the finite-size effect on transport properties under periodic boundary conditions. This conclusion is in accord with the established experimental results of ionic liquids.