Characterizing Microheterogeneity in Liquid Mixtures via Local Density Fluctuations

Abstract

We present a novel approach to characterize and quantify microheterogeneity and microphase separation in computer simulations of complex liquid mixtures. Our post-processing method is based on local density fluctuations of the different constituents in sampling spheres of varying size. It can be easily applied to both molecular dynamics (MD) and Monte Carlo (MC) simulations, including periodic boundary conditions. Multidimensional correlation of the density distributions yields a clear picture of the domain formation due to the subtle balance of different interactions. We apply our approach to the example of force field molecular dynamics simulations of imidazolium-based ionic liquids with different side chain lengths at different temperatures, namely 1-ethyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, and 1-decyl-3-methylimidazolium chloride, which are known to form distinct liquid domains. We put the results into the context of existing microheterogeneity analyses and demonstrate the advantages and sensitivity of our novel method. Furthermore, we show how to estimate the configuration entropy from our analysis, and we investigate voids in the system. The analysis has been implemented into our program package TRAVIS and is thus available as free software.

Keywords

• ionic liquids
• microheterogeneity
• voids
• molecular dynamics
• Monte Carlo
• liquid phase