Accurate prediction of ionic liquid density-of-states from low-cost calculations

Fogarty, R. M., Matthews, R. P., Hunt, P. A. and Lovelock, K. R. J. ORCID: https://orcid.org/0000-0003-1431-269X (2025) Accurate prediction of ionic liquid density-of-states from low-cost calculations. Physical Chemistry Chemical Physics. ISSN 1463-9084 doi: 10.1039/D5CP00214A (In Press)

Abstract/Summary

The electronic structure of ionic liquids (ILs) is a key factor in their chemical reactivity. Experimental techniques provide insight into IL electronic structure (e.g. X-ray photoelectron spectroscopy, XPS), but are impractical for screening large numbers of potential ILs. Computational screening offers an alternative approach, but current ab initio calculation methods (ion-pairs or large calculations with periodic boundaries) are not suitable for screening. We establish that a simple and computationally low-cost method, lone-ions evaluated at the B3LYP-D3(BJ)/6-311+G(d,p) level employing a generalised solvation model SMD (Solvation Model based on Density), captures IL liquid-phase density-of-states (DoS) with good accuracy by validating against XPS data for a wide range of ILs. The additivity of the results from individual lone-ion calculations provides a significant advantage, enabling predictions of the DoS for a large number of ILs and delivering a significant step towards the computational screening of ILs for many applications.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/122083
Identification Number/DOI	10.1039/D5CP00214A
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Publisher	Royal Society of Chemistry
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