Quantum chemical calculations of formation enthalpies of cations and anions of ionic liquids

• Published in: Journal of molecular liquids 2022-10, Vol.364, p.119996, Article 119996
• Main Authors: Govorov, Dmitrii N., Dunaev, Anatoliy M., Motalov, Vladimir B., Kudin, Lev S.
• Format: Article
• Language: English
• Subjects: Anion; Cation; Formation enthalpy; Ionic liquid; Isodesmic reactions; Quantum chemical calculation
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2022.119996

[Display omitted] •ΔfH° of imidazolium cations CnMIm+ (n = 2, 4, 6, 8, 10) were determined by quantum chemical calculations.•ΔfH° of trifluoromethanesulfonate, ethyl sulfate, dicyanamide, and bis(trifluoromethane)sulfonylimide anions were also found.•The enthalpies of heterolytic dissociation of neutral ion pairs were derived.•G4 method was found to be most appropriate for describing the thermodynamic quantities of the ions of ionic liquids. The development of advanced ionic-liquid-based applications requires accurate thermochemical data for both ionic liquids and their constituent ions. Herein, the formation enthalpies of alkylimidazolium cations ([CnMIm+], n = 2, 4, 6, 8, 10) and various anions (trifluoromethanesulfonate ([TfO−]), ethyl sulfate ([ES−]), dicyanamide ([DCA−]), and bis(trifluoromethane)sulfonylimide ([NTf2−])) in the ideal gas state were obtained by quantum chemical calculations using density functional theory (DFT: B3LYP, B98, M06, M06-2X) and composite (G4) thermochemical models in the framework of the isodesmic reaction approach. The enthalpies of heterolytic dissociation of neutral ion pairs (NIPs) for the [CnMIm+][X−] series (n = 2, 4, 6, 8, 10; X− = [TfO−], [ES−], [NTf2−], [DCA−], [BF4−], [PF6−], [Cl−], [Br−], [I−]) were derived using the obtained data and literature formation enthalpies (ΔfH°) of NIPs. Analysis of the thermochemical property trends revealed that the formation enthalpies of [CnMIm+] decrease linearly as the alkyl chain length increases. In addition, the use of the isodesmic reaction approach improved the reliability of the computed data. Furthermore, owing to its internal self-consistency, the G4 method was found to be the most appropriate for describing the thermodynamic quantities of the cations and anions of ionic liquids.