DFT study of the energetic and noncovalent interactions between imidazolium ionic liquids and hydrofluoric acid
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In this work, we evaluated the energetic interactions between imidazolium ionic liquids (ILs) and hydrofluoric acid, as well as the cation-anion interactions in ILs. We used DFT calculations that include dispersion corrections employing the PBE and M06 functionals. We tested 22 ILs, including [C4MIM][PF6], [C4MIM][NTf2], and [C4MIM][CH3COO], obtaining interaction energies in the range of -27 to -13 kcal/mol with the PBE functional. The NCI (noncovalent interaction) index developed by Yang and collaborators (J. Am. Chem. Soc. 2010, 132, 6498-6506; J. Chem. Theory Comput. 2011, 7, 625-632) also was used for mapping the key noncovalent interactions (hydrogen bonds, van der Waals, and steric repulsions) between the anions and cations of ILs and also for interactions of ILs with hydrofluoric acid (HF). The results obtained show that the anions have a stronger effect with respect to cations in their capacity for interacting with hydrofluoric acid, and the strongest interaction energies occur in systems where the key noncovalent interactions are mainly hydrogen bonds. The [C4MIM][PF6], [C4MIM][NTf2], and [C4MIM][BF4] ionic liquids displayed the weakest cation-anion interactions. © 2015 American Chemical Society.
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Hydrofluoric acid; Hydrogen bonds; Ions; Liquids; Negative ions; Positive ions; Van der Waals forces; Cation-anion interactions; DFT calculation; Dispersion correction; Imidazolium ionic liquids; Interaction energies; Non-covalent interaction; Steric repulsions; Van der waals; Ionic liquids
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