Cohesive Properties of Ionic Liquids Calculated from
First Principles
Posted on 2019-09-04 - 21:29
Low volatility of ionic liquids (ILs),
being one of their most
valuable properties, is also the principal factor making reliable
measurements of vapor pressures and vaporization (or sublimation)
enthalpies of ILs extremely difficult. Alternatively, vaporization
enthalpies at the temperature of the triple point can be obtained
from the enthalpies of sublimation and fusion. While the latter can
be obtained calorimetrically with a fair accuracy, the former is in
principle accessible through ab initio computations. This work assesses
the performance of the first-principles calculations of sublimation
properties of ILs. Namely, 3 compounds, coupling the 1-ethyl-3-methylimidazolium
cation [emIm] with either tetrafluoroborate [BF4], hexafluorophosphate
[PF6], or bis(trifluoromethylsulfonyl)imide [NTf2] anions were selected for a case study. A computational methodology,
originally developed for molecular crystals, is adopted for crystals
of ILs. It exploits periodic density functional theory (DFT) calculations
of the unit-cell geometries and quasi-harmonic phonons and many-body
expansion schemes for ab initio refinements of the lattice energies
of crystalline ILs. The vapor phase is treated as the ideal gas whose
properties are obtained combining the rigid rotor–harmonic
oscillator model with corrections from the one-dimensional hindered
rotors and molecular-dynamics simulations capturing the contributions
from the interionic interaction modes. Although the given computational
approach enables one to reach the chemical accuracy (4 kJ mol–1) of calculated sublimation enthalpies of simple molecular
crystals, reaching the same level of accuracy for ionic liquids proves
challenging as crystals of ionic liquids are bound appreciably stronger
than common molecular crystals, the underlying cohesive energies of
solid ionic liquids is up to 1 order of magnitude larger. Still, combination
of the mentioned computational and experimental frameworks results
in a novel promising scheme that is expected to generate reliable
and accurate temperature-dependent data on sublimation (and vaporization)
of ILs.
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Červinka, Ctirad; Klajmon, Martin; Štejfa, Vojtěch (2019). Cohesive Properties of Ionic Liquids Calculated from
First Principles. ACS Publications. Collection. https://doi.org/10.1021/acs.jctc.9b00625