Comparison of the effective fragment potential method with symmetry-adapted perturbation theory in the calculation of intermolecular energies for ionic liquids

Samuel Y S Tan, Ekaterina I. Izgorodina

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Abstract

The effective fragment potential (EFP) method that decomposes the interaction energy as a sum of the five fundamental forces - electrostatic, exchange-repulsion, polarization, dispersion, and charge transfer - was applied to a large test set of ionic liquid ion pairs and compared against the state-of-the-art method, Symmetry-Adapted Perturbation Theory (SAPT). The ion pairs include imidazolium and pyrrolidinium cations combined with anions that are routinely used in the field of ionic liquids. The aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(d,p) basis sets were used for EFP, while SAPT2+3/aug-cc-pVDZ provided the benchmark energies. Differences between the two methods were found to be large, and strongly dependent on the anion type. For the aug-cc-pVTZ basis set, which produced the least errors, average relative errors were between 2.3% and 18.4% for pyrrolidinium ion pairs and between 2.1% and 27.7% for imidazolium ion pairs for each individual energetic component (excluding charge transfer), as well as the total interaction energy. Charge transfer gave the largest relative errors: 56% and 63% on average for pyrrolidinium- and imidazolium-based ion pairs, respectively. Scaling of the EFP components against SAPT2+3 showed improvement for polarization (induction) and dispersion terms, thus indicating potential for the development of cost-effective alternatives for intermolecular induction and dispersion potentials for ionic liquids.

Original languageEnglish
Pages (from-to)2553-2568
Number of pages16
JournalJournal of Chemical Theory and Computation
Volume12
Issue number6
DOIs
Publication statusPublished - 14 Jun 2016

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