Effect of Ion Mass on Dynamic Correlations in Ionic Liquids

Ionic liquids (ILs) are a class of liquid salts with distinct properties such as high ionic conductivity, low volatility, and a broad electrochemical window, making them appealing for use in energy storage applications. The ion-ion correlations are some of the key factors that play a critical role in the ionic conductivity of ILs. In this work, we present the study of the impact of ion mass on ion-ion correlations in ILs, applying a combination of broadband dielectric spectroscopy measurements and molecular dynamics simulations. We examined three ILs with the same cation but different anions to consider three different cases of cation-anion masses: M₊ > M_-, M₊ ≈ M_-, and M₊ < M_-. We applied the momentum conservation approach to estimate the contribution of distinct ion-ion correlations from experimental data and obtained good agreement with direct calculations of distinct ion-ion correlations from molecular dynamics simulations. Our findings reveal that relative ion mass has a strong effect on the distinct ion-ion correlations, leading to swapping of the relative amplitude of distinct cation-cation and anion-anion correlations.