Establishing the accuracy of density functional approaches for the description of noncovalent interactions in ionic liquids
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Gould, Tim
Izgorodina, Ekaterina I
Rocca, Dario
Lebègue, Sébastien
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Abstract
We test a number of dispersion corrected versatile Generalized Gradient Approximation (GGA) and meta-GGA functionals for their ability to predict the interactions of ionic liquids, and show that most can achieve energies within 1 kcal mol-1 of benchmarks. This compares favorably with an accurate dispersion corrected hybrid, ωB97X-V. Our tests also reveal that PBE (Perdew-Burke-Ernzerhof GGA) calculations using the plane-wave projector augmented wave method and Gaussian Type Orbitals (GTOs) differ by less than 0.6 kJ mol-1 for ionic liquids, despite ions being difficult to evaluate in periodic cells - thus revealing that GTO benchmarks may be used also for plane-wave codes. Finally, the relatively high success of explicit van der Waals density functionals, compared to elemental and ionic dispersion models, suggests that improvements are required for low-cost dispersion correction models of ions.
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Physical Chemistry Chemical Physics
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23
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45
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Chemical sciences
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Kim, M; Gould, T; Izgorodina, EI; Rocca, D; Lebègue, S, Establishing the accuracy of density functional approaches for the description of noncovalent interactions in ionic liquids, Physical Chemistry Chemical Physics, 2021, 23 (45), pp. 25558-25564