A combined QTAIM, DFT and molecular dynamics study on the nanoscale dynamical and structural organization of imidazolium-based dicationic ionic liquids

In this work, the effects of linkage alkyl chain length on the dynamical and structural micro-heterogeneities of some imidazolium-based dicationic ionic liquids (DILs) i.e. [Cn(mim)2][BF4]2, (n = 3, 6, 9, and 12) were studied via quantum mechanical calculations and also classical molecular dynamics (MD) simulations. Hydrogen bondings and also the interaction energies between the studied ions have been calculated using the density functional theory (DFT) calculations and also the quantum theory of atoms in molecules (QTAIM) method. The results showed that with increasing the linkage alkyl chain length of DILs, the interaction energies and electron densities are decreased, because the electro-static interactions in DILs are weakened with increasing the -CH2 groups in the linkage chain. Different kinds of combined distribution functions (CDFs) were computed to better understand the ori-entations of ions in the studied DILs. Although, two rings of cation are almost perpendicular with respect to each other in all studied DILs, the orientation of linkage chain with respect to the rings is different in short-and long-linkage chain DILs. To understand the arrangement of the nearest neighboring ions, neighborhood analysis and spatial distribution functions (SDFs) of ions were analyzed. Furthermore, the mean square displacement (MSD), non-Gaussian parameter, van Hove correlation of cation and anions and also the ion pair, ion cage, hydrogen bond and reorientation dynamics were computed. DILs with longer alkyl chain length have more deviation in non-Gaussian parameter and Gaussian behav-ior of distribution of particle displacements, probably due to weakening the electrostatic interactions. Also, they have higher ion cage/ion pair stabilities than DILs with shorter linkage chain. Altogether, the linkage chain length in DILs has significant influences on their organizations in such a way that with increasing linkage chain length, their dynamical and structural micro-heterogeneities increase. (C) 2022 Elsevier B.V. All rights reserved.