Establishing the accuracy of density functional approaches for the description of noncovalent interactions in ionic liquids

Minho Kim, Tim Gould, Ekaterina I. Izgorodina, Dario Rocca, Sébastien Lebègue

Research output: Contribution to journalArticleResearchpeer-review

5 Citations (Scopus)

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. This journal is

Original languageEnglish
Pages (from-to)25558-25564
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number45
DOIs
Publication statusPublished - 7 Dec 2021

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