Accurate Prediction of Ionic Liquid Density-of-States from Low-Cost Calculations

Article


Fogarty, R., Matthews, R. P., Hunt, P. A. and Lovelock, K. R. J. 2025. Accurate Prediction of Ionic Liquid Density-of-States from Low-Cost Calculations. Physical Chemistry Chemical Physics. p. In press. https://doi.org/10.1039/D5CP00214A
AuthorsFogarty, R., Matthews, R. P., Hunt, P. A. and Lovelock, K. R. J.
Abstract

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.

JournalPhysical Chemistry Chemical Physics
Journal citationp. In press
ISSN1463-9084
Year2025
PublisherRoyal Society of Chemistry
Accepted author manuscript
License
File Access Level
Anyone
Digital Object Identifier (DOI)https://doi.org/10.1039/D5CP00214A
Publication dates
Online21 Mar 2025
Publication process dates
Deposited04 Apr 2025
Accepted19 Mar 2025
Copyright holder© 2025 The Authors
Permalink -

https://repository.uel.ac.uk/item/8z4w3

Download files


Accepted author manuscript
d5cp00214a.pdf
License: CC BY 4.0
File access level: Anyone

  • 35
    total views
  • 21
    total downloads
  • 8
    views this month
  • 2
    downloads this month

Export as

Related outputs

Efficient Prediction of the Local Electronic Structure of Ionic Liquids from Low-Cost Calculations
Tompkins, F. T., Parker, L., Fogarty, R., Seymour, J., Rowe, R., Palgrave, R., Matthews, R. P., Bennett, R., Hunt, P. A. and Lovelock, K. R. J. 2025. Efficient Prediction of the Local Electronic Structure of Ionic Liquids from Low-Cost Calculations. Physical Chemistry Chemical Physics. p. In press. https://doi.org/10.1039/D5CP00892A
New directions in experiment and theory, interfaces, and interactions: general discussion
Atkin, R., Bruce, D. W., Dryfe, R. A. W., Dubois, E., Edler, K. J., Elgar, C. E., Feeney, A., Goloviznina, K., Groves, T. S., Hansen, B., Holbrey, J. D., Holm, C., Kornyshev, A., Margulis, C. J., Markiewitz, D. M., Matthews, R., Maurer, J., Miao, S., Philippi, F., Rezabal, E., Roling, B., Rotenberg, B., Sangoro, J., Schönhoff, M., Slattery, J. M., Swadźba-Kwaśny, M., Taylor, N., Watanabe, M. and Yang, J. 2024. New directions in experiment and theory, interfaces, and interactions: general discussion. Faraday Discussions. 253, pp. 493-509. https://doi.org/10.1039/D4FD90037E
Controlling and predicting alkyl-onium electronic structure
Towers Tompkins, F. K., Parker, L. G., Fogarty, R. M., Seymour, J. M., Gousseva, E., Grinter, D. C., Palgrave, R. G., Smith, C. D., Bennett, R. A., Matthews, R. and Lovelock, K. R. J. 2024. Controlling and predicting alkyl-onium electronic structure. Chemical Communications. (60), p. 10756–10759. https://doi.org/10.1039/D4CC03388D
Unravelling the complex speciation of halozincate ionic liquids using X-ray spectroscopies and calculations
Seymour, J., Gousseva, E., Towers Tompkins, F., Parker, L., Alblewi, N., Clarke, C. J., Hayama, S., Palgrave, R., Bennett, R., Matthews, R. P. and Lovelock, K. R. J. 2024. Unravelling the complex speciation of halozincate ionic liquids using X-ray spectroscopies and calculations. Faraday Discussions. 253, pp. 251-272. https://doi.org/10.1039/D4FD00029C
Exploiting Cation Structure and Water Content in Modulating the Acidity of Ammonium Hydrogen Sulfate Protic Ionic Liquids
Firth, A. E. J., Nakasu, P. Y. S., Hallett, J. P. and Matthews, R. P. 2024. Exploiting Cation Structure and Water Content in Modulating the Acidity of Ammonium Hydrogen Sulfate Protic Ionic Liquids. The Journal of Physical Chemistry Letters. 15 (9), pp. 2311-2318. https://doi.org/10.1021/acs.jpclett.3c03583
Unveiling the Rational Development of Stimuli-Responsive Silk Fibroin-Based Ionogel Formulations
Shmool, T. A., Martin, L. K., Jirkas, A., Matthews, R. P., Constantinou, A. P., Vadukul, D. M., Georgiou, T. K., Aprile, F. A. and Hallett, J. P. 2023. Unveiling the Rational Development of Stimuli-Responsive Silk Fibroin-Based Ionogel Formulations. Chemistry of Materials. 35 (15), p. 5798–5808. https://doi.org/10.1021/acs.chemmater.3c00303