The validity of the Stokes-Einstein relation in ionic liquids

RESUMO

Ionic liquids (ILs) exhibit supercooled liquids behavior even above room temperature and the Stokes-Einstein (SE) relation is often considered to be invalid in ILs as that in supercooled liquids. However, the conclusion is usually drawn based on some variants of SE relation. In this work, we have systematically investigated the validity of the Stokes-Einstein relation in ILs by performing molecular dynamics simulations of coarse-grained IL within the temperature range of 400-800 K. Both the original SE formulation, and two commonly employed variants, were examined to assess their applicability and consistency. These three formulas yield distinctly different results, indicating that the two variants are not reliable substitutes for the original SE relation. The inconsistency suggests the fact that the r in Stokes law varies with conditions. The breakdown arises from the ion correlations introduced by the strong electrostatic interactions. This proposition is further confirmed by simulations.