Correlation-Based Predictions of Gas Solute Diffusivity in Ionic Liquid Solvents Based on Solvent-Accessible Surface...

In our prior study [Olowookere, F. V.; Turner, C. H. J. Phys. Chem. B 2023, 127(42), 9144-9154], we introduced a new scaling relationship to predict gas solute diffusion at challenging conditions, focusing on CO₂ and SO₂ diffusion in multivalent ionic liquid (IL) solvents. This work extends our initial exploratory study into a much broader array of systems, encompassing additional solutes (N₂, CH₄, C₂H₆, C₃H₈, C₃H₈O, and H₂O) and a variety of different ionic liquid species ([Bzmim₃]³⁺, [Bzmim₄]⁴⁺, [BMIM]⁺, [EMIM]⁺, [HMIM]⁺, [NapO₂]^2-, [BzO₃]^3-, [BF₄]^-, [Tf₂N]^-, and [PF₆]^-). Our study demonstrates a remarkably robust logarithmic correlation between solute diffusion and solvent accessible surface area (SA) across 20 different additional systems. We perform comprehensive analyses of the underlying molecular phenomena responsible for this correlation, including solute lifetime distributions, void space dynamics, and Voronoi tessellation, in order to elucidate a stronger mechanistic understanding of this behavior. Our findings highlight a direct link between the solvent accessible SA and the size of the void domains. Overall, our scaling approach provides an efficient and reliable approach for predicting diffusion from analyses of short simulations at higher temperatures.