Density Functional Theory Descriptors for Ionic Liquids and the Introduction of a Coulomb Correction

Frederik Philippi; Anna Quinten; Daniel Rauber; Michael Springborg; Rolf Hempelmann

doi:10.1021/acs.jpca.9b01831

Density Functional Theory Descriptors for Ionic Liquids and the Introduction of a Coulomb Correction

J Phys Chem A. 2019 May 16;123(19):4188-4200. doi: 10.1021/acs.jpca.9b01831. Epub 2019 May 2.

Authors

Frederik Philippi¹, Anna Quinten¹, Daniel Rauber^{1

2}, Michael Springborg^{3

4}, Rolf Hempelmann^{1

2}

Affiliations

¹ Physical Chemistry , Saarland University , Campus B 2 2 , 66123 Saarbrücken , Germany.
² Transfercenter Sustainable Electrochemistry , Saarland University and KIST Europe , Am Markt, Zeile 3 , 66125 Saarbrücken , Germany.
³ Physical and Theoretical Chemistry , Saarland University , Campus B 2 2 , 66123 Saarbrücken , Germany.
⁴ School of Materials Science and Engineering , Tianjin University , Tianjin 300072 , P. R. China.

PMID: 30991004
DOI: 10.1021/acs.jpca.9b01831

Abstract

As a result of continuing ionic liquid research, it becomes clearer that charge transfer in ionic liquids has a physical reality. In a recent publication, we demonstrated the utility of simple density functional theory descriptors to estimate charge transfer for a large number of ion combinations, which is possible because the ions are treated separately. A major disadvantage found was that the charge transfer was systematically overestimated. In this work, we introduce a correction to account for the losses in Coulomb attraction when charge is transferred from the anion to the cation. We find that accounting for these losses is important to describe charge transfer in ionic liquids appropriately. The advantage that the calculations can be performed separately on the individual, isolated ions is maintained. The corrected as well as the uncorrected charge transfer have been calculated for over 4000 cation-anion combinations at the R(O)B3LYP/6-311+G(2d,p)//RB3LYP/6-31+G(d,p) level of theory. With the correction, the absolute values for the charge transfer are no longer unrealistically high and agree well with other charge transfer estimates from the literature. In general, the cumulative nature of the Haven ratio is now correctly mirrored in the relationship between the corrected theoretical charge transfer and the experimental estimate from the Nernst-Einstein relation. Earlier findings on the similarities between ether-functionalized and nonfunctionalized ionic liquids are confirmed. However, we also observe inconsistencies when using the experimental charge transfer estimates together with the ionicity interpretation of the Haven ratio. These can be interpreted as a hint toward the latter premise being wrong.