Comparative assessment of the performance of density functionals and dispersion correction on different properties of dicationic ionic liquids – an ab initio molecular dynamics (AIMD) study

Abstract

In this study, we investigated the effect of DFT density functionals and dispersion correction on an imidazolium-based dicationic ionic liquid (DIL) using ab initio molecular dynamics simulations. To achieve this purpose, the electronic structures, as well as the structural and dynamical properties of [C₃(mim)₂][NTF₂]₂ DIL, were obtained using the BLYP and PBE functionals, both with and without D3-correction, and the results were compared with experimental values. Radial distribution functions and structure factors revealed that applying D3-correction increases the interaction between the anion and hydrogen atoms of the rings and side chains. The simulation of the studied DIL with the BLYP-D3 functional depicted lower structural heterogeneity compared to the other functionals. Analysis of Voronoi tessellation and linkage chain conformations showed a reduction in the aggregation of the linkage alkyl chains in the presence of D3-correction, which is more pronounced in the BLYP functional than in PBE. Additionally, it was observed that the probability of forming a hydrogen-bond network depends on both the type of used density functionals and applying dispersion correction. The results of dynamical properties, such as the self-diffusion coefficients, velocity autocorrelation function, and van Hove correlation function, as well as ion pair, ion cage, and hydrogen bond dynamics, indicated that applying D3-correction in both density functionals leads to an increase in the dynamics of the studied DIL. Additionally, the ratio of self-diffusion coefficients of the anion to the cation in the BLYP functional is closer to experimental values compared to the PBE functional. Furthermore, the electronic structure, including dipole moment distribution, and also infrared (IR) and power spectra were studied. Applying D3-correction and the type of density functionals have a significant effect on the dipole moment distribution of ions. Moreover, the results of IR and power spectra demonstrated that only in the BLYP functional, by applying D3-correction, the hydrogen bonding between the anion and the hydrogen atoms of the cation is strengthened at high wavenumbers. Thus, we conclude that applying D3 correction to both the BLYP and PBE density functionals improves the accuracy in describing the various properties of the studied system. Overall, the evaluation of different structural, dynamical, and vibrational properties of [C₃(mim)₂][NTF₂]₂ DIL suggests that the BLYP-D3 density functional may be the best choice among the studied density functionals.