Core-level binding energies describe electrostatic potentials at nuclei for ionic liquids

Towers Tompkins, F. K., Gousseva, E., Bennett, R. A. ORCID: https://orcid.org/0000-0001-6266-3510, Grau-Crespo, R. ORCID: https://orcid.org/0000-0001-8845-1719 and Lovelock, K. R. J. ORCID: https://orcid.org/0000-0003-1431-269X (2025) Core-level binding energies describe electrostatic potentials at nuclei for ionic liquids. Physical Chemistry Chemical Physics, 27 (41). pp. 22004-22012. ISSN 1463-9084 doi: 10.1039/d5cp02411k

Abstract/Summary

Electrostatic interactions in ionic liquids (ILs) dictate many of their physical properties and hence underpin a plethora of potential applications. It is vital to develop both experimental and theoretical electronic descriptors for ILs, to drive deeper understanding of the interactions that may be tuned for applications. A possible descriptor for ILs is the readily measurable core-level binding energy from experimental core-level X-ray photoelectron spectroscopy (XPS), EB(core). To establish that differences in EB(core) capture the differences in electrostatic potential at nuclei, Vn, we use a computational approach based on ab initio molecular dynamics (AIMD). We demonstrate clear quantitative (linear) correlations between experimental EB(core) and calculated Vn for carbon, nitrogen, sulfur, oxygen and fluorine for both cations and anions. Our work shows that EB(core) are chemically interpretable descriptors of electrostatic interactions in ILs. This has implications for the ability to predict, out of the vast number of ILs that can form from the array of available cations and anions, the best IL compositions for target applications. We also discuss how this work could open up new areas of enquiry, and the potential usefulness of Vn to characterise interactions of ILs with surfaces and interfaces.

Item Type	Article
URI	https://centaur.reading.ac.uk/id/eprint/125151
Identification Number/DOI	10.1039/d5cp02411k
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Publisher	Royal Society of Chemistry
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