Uncovering the Properties of Dicationic Ionic Liquid Nanodroplets through Ab Initio Molecular Dynamics Simulations

ZO Memar and M Moosavi, JOURNAL OF PHYSICAL CHEMISTRY B, 127, 9111-9131 (2023).

DOI: 10.1021/acs.jpcb.3c03585

The behavior of nanodroplets of an imidazolium-based dicationic ionic liquid, i.e., C-1(mim)(2)PF6(2), was investigated in this study using ab initio molecular dynamics simulations. The vibrational features as well as the structural, interfacial, and dynamical properties of different sized droplets were analyzed and compared to the bulk phase system. Structural properties of the droplets, such as pi-pi stacking, radial distribution functions, structure factors, combined distribution functions, and angular distribution functions were analyzed to understand the interactions and orientations of their ions. The vibrational features and hydrogen bonding strength of droplets were studied by calculating their infrared (IR) and power spectra, determining the contribution of different types of hydrogen bonding to each vibrational mode. The calculated spectra showed good overall agreement with the experimental results. The interfacial properties of the droplets and the orientation of their ions were analyzed using density profiles and an exposed surface. The results showed that, in all systems studied, cations and anions were equally likely to exist in both inner and outer layers, and the cations tended to be oriented toward the center of droplets with obtuse angles. Additionally, the droplet densities were extrapolated to predict the bulk phase density with less than 2% deviation. The dynamical properties of hydrogen bonds, mean square displacement, and van Hove correlations of cations and anions were also analyzed. The results indicated that there was no regular trend in the dynamic properties of droplets with an increasing system size.

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