Effect of Relative Mass on Ion Velocity Cross-Correlations in Ionic Liquids and Molten Salts: Different Perspectives in Different Reference Frames

Abstract

In electrolytes, the self-and interdiffusion coefficients, transport numbers, and electrical conductivity can be used to determine velocity cross-correlation coefficients (VCC) that are also accessible through molecular dynamics simulations. In an ionic liquid or molten salt, there are only three, corresponding to correlations between the velocities of distinct ion pairs (cation− anion, cation−cation, and anion−anion) averaged over both the ensemble and time, calculable from experimental ion self-diffusion coefficients and the electrolyte conductivity. Most usually, the mass-fixed frame of reference (with velocities relative to that of the center of mass of the system) is used to discuss the VCC and the distinct diffusion coefficients (DDC) derived from them. Recent work in the literature has suggested a dependence of the DDC on the ratio of the anion to cation mass. Here, we demonstrate, using our own and literature transport property data for a large number of ionic liquids and molten salts, that the trends observed depend on the particular choice of velocity reference frame, mass-, number-, or volume-fixed. The perception of ion−ion interactions may be distorted in the mass-and volume fixed frames when the co-ions have very different masses or volumes, particularly for systems containing light lithium ions.