Ekaterina Gousseva
Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory
Gousseva, Ekaterina; Towers Tompkins, Frances K.; Seymour, Jake M.; Parker, Lewis G.; Clarke, Coby J.; Palgrave, Robert G.; Bennett, Roger A.; Grau-Crespo, Ricardo; Lovelock, Kevin R.J.
Authors
Frances K. Towers Tompkins
Jake M. Seymour
Lewis G. Parker
COBY CLARKE Coby.Clarke@nottingham.ac.uk
Research Fellow
Robert G. Palgrave
Roger A. Bennett
Ricardo Grau-Crespo
Kevin R.J. Lovelock
Abstract
Using a combination of experiments and calculations, we have gained new insights into the nature of anion-cation interactions in ionic liquids (ILs). An X-ray photoelectron spectroscopy (XPS)-derived anion-dependent electrostatic interaction strength scale, determined using XPS core-level binding energies for IL cations, is presented here for 39 different anions, with at least 18 new anions included. Linear correlations of experimental XPS core-level binding energies for IL cations with (a) calculated core binding energies (ab initio molecular dynamics (AIMD) simulations were used to generate high-quality model IL structures followed by single-point density functional theory (DFT) to obtain calculated core binding energies), (b) experimental XPS core-level binding energies for IL anions, and (c) other anion-dependent interaction strength scales led to three main conclusions. First, the effect of different anions on the cation can be related to ground-state interactions. Second, the variations of anion-dependent interactions with the identity of the anion are best rationalized in terms of electrostatic interactions and not occupied valence state/unoccupied valence state interactions or polarizability-driven interactions. Therefore, the XPS-derived anion-dependent interaction strength scale can be explained using a simple electrostatic model based on electrostatic site potentials. Third, anion-probe interactions, irrespective of the identity of the probe, are primarily electrostatic, meaning that our electrostatic interaction strength scale captures some inherent, intrinsic property of anions independent of the probe used to measure the interaction strength scale.
Citation
Gousseva, E., Towers Tompkins, F. K., Seymour, J. M., Parker, L. G., Clarke, C. J., Palgrave, R. G., Bennett, R. A., Grau-Crespo, R., & Lovelock, K. R. (2024). Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory. Journal of Physical Chemistry B, 128(20), 5030-5043. https://doi.org/10.1021/acs.jpcb.4c00362
Journal Article Type | Article |
---|---|
Acceptance Date | Apr 22, 2024 |
Online Publication Date | May 10, 2024 |
Publication Date | May 23, 2024 |
Deposit Date | Jul 31, 2024 |
Publicly Available Date | Aug 6, 2024 |
Journal | Journal of Physical Chemistry B |
Print ISSN | 1520-6106 |
Electronic ISSN | 1520-5207 |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 128 |
Issue | 20 |
Pages | 5030-5043 |
DOI | https://doi.org/10.1021/acs.jpcb.4c00362 |
Public URL | https://nottingham-repository.worktribe.com/output/34634144 |
Publisher URL | https://pubs.acs.org/doi/10.1021/acs.jpcb.4c00362 |
Files
Anion-Dependent Strength Scale of Interactions
(6.9 Mb)
PDF
Publisher Licence URL
https://creativecommons.org/licenses/by/4.0/
You might also like
Thermally-Stable Imidazolium Dicationic Ionic Liquids with Pyridine Functional Groups
(2020)
Journal Article
Thermolysis of Organofluoroborate Ionic Liquids to NHC-Organofluoroborates
(2020)
Journal Article
Experimental measurement and prediction of ionic liquid ionisation energies
(2021)
Journal Article
Downloadable Citations
About Repository@Nottingham
Administrator e-mail: discovery-access-systems@nottingham.ac.uk
This application uses the following open-source libraries:
SheetJS Community Edition
Apache License Version 2.0 (http://www.apache.org/licenses/)
PDF.js
Apache License Version 2.0 (http://www.apache.org/licenses/)
Font Awesome
SIL OFL 1.1 (http://scripts.sil.org/OFL)
MIT License (http://opensource.org/licenses/mit-license.html)
CC BY 3.0 ( http://creativecommons.org/licenses/by/3.0/)
Powered by Worktribe © 2024
Advanced Search