Exploring enthalpies of formation of imidazolium-, pyridinium-, and pyrrolidinium-based ionic liquids with dicyanamide anion using quantum chemical methods

摘要

In this work, quantum chemical calculations have been performed on the ionic liquids based on imidazolium, pyridinium, and pyrrolidinium cations with the dicyanamide anion. The dispersion-corrected B3LYP exchange-correlation functional was used to optimize geometries. Enthalpies of formation were calculated at the high-level G3(MP2) theory by employing both the atomization energy and reaction enthalpy approaches. There exists a very good agreement between the predicted enthalpies of formation and available experimental values. For the first time, the enthalpies of formation have been predicted for 21 ion pairs with no available experimental data. The calculated enthalpies of formation are decreased with increasing alkyl chain length. Linear correlations were observed between enthalpy of formation and number of carbon atoms in the alkyl side-chain for all of the studied series of cations. Regardless of the cation type, the contribution of each CH2 group in the alkyl chain to the enthalpy of formation was also determined. (C) 2020 Elsevier B.V. All rights reserved.