Issue 17, 2025

Efficient prediction of the local electronic structure of ionic liquids from low-cost calculations

Abstract

Understanding and predicting ionic liquid (IL) electronic structure is crucial for their development, as local, atomic-scale electrostatic interactions control both the ion–ion and ion–dipole interactions that underpin all applications of ILs. Core-level binding energies, EB(core), from X-ray photoelectron spectroscopy (XPS) experiments capture the electrostatic potentials at nuclei, thus offering significant insight into IL local electronic structure. However, our ability to measure XPS for the many thousands of possible ILs is limited. Here we use an extensive experimental XPS dataset comprised of 44 ILs to comprehensively validate the ability of a very low-cost and technically accessible calculation method, lone-ion-SMD (solvation model based on density) density functional theory (DFT), to produce high quality EB(core) for 14 cations and 30 anions. Our method removes the need for expensive and technically challenging calculation methods to obtain EB(core), thus giving the possibility to efficiently predict local electronic structure and understand electrostatic interactions at the atomic scale. We demonstrate the ability of the lone-ion SMD method to predict the speciation of halometallate anions in ILs.

Graphical abstract: Efficient prediction of the local electronic structure of ionic liquids from low-cost calculations

Supplementary files

Article information

Article type
Paper
Submitted
06 Mar 2025
Accepted
17 Mar 2025
First published
18 Mar 2025
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2025,27, 8803-8812

Efficient prediction of the local electronic structure of ionic liquids from low-cost calculations

F. K. Towers Tompkins, L. G. Parker, R. M. Fogarty, J. M. Seymour, R. Rowe, R. G. Palgrave, R. P. Matthews, R. A. Bennett, P. A. Hunt and K. R. J. Lovelock, Phys. Chem. Chem. Phys., 2025, 27, 8803 DOI: 10.1039/D5CP00892A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements