Predicting Gaseous Solute Diffusion in Viscous Multivalent Ionic Liquid Solvents.

Abstract

Calculating solute diffusion in dense, viscous solvents can be particularly challenging in molecular dynamics simulations due to the long time scales involved. Here, a new scaling approach is developed for predicting solute diffusion based on analyses of CO2 and SO2 diffusion in two different multivalent ionic liquid solvents. Various scaling approaches are initially evaluated, including single and separate thermostats for the solute and solvent, as well as the application of the Arrhenius relationship and the Speedy-Angell power law. A very strong logarithmic correlation is established between the solvent-accessible surface area and solute diffusion. This relationship, reflecting Danckwerts' surface renewal theory and the Vrentas-Duda free volume model, presents a valuable method for estimating diffusion behavior from short simulation trajectories at elevated temperatures. The approach may be beneficial for enhancing predictive modeling in similar challenging systems and should be more broadly evaluated.