Experimental validation of calculated atomic charges in ionic liquids

Publication available at: http://eprints.whiterose.ac.uk/125903/
Title: Experimental validation of calculated atomic charges in ionic liquids
Author(s): Fogarty, RM
Matthews, RP
Ashworth, CR
Brandt-Talbot, A
Palgrave, RG
Bourne, RA
Hoogerstraete, TV
Hunt, PA
Lovelock, KRJ
Item Type: Journal Article
Abstract: A combination of X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure spectroscopy has been used to provide an experimental measure of nitrogen atomic charges in nine ionic liquids (ILs). These experimental results are used to validate charges calculated with three computational methods: charges from electrostatic potentials using a grid-based method (ChelpG), natural bond orbital population analysis, and the atoms in molecules approach. By combining these results with those from a previous study on sulfur, we find that ChelpG charges provide the best description of the charge distribution in ILs. However, we find that ChelpG charges can lead to significant conformational dependence and therefore advise that small differences in ChelpG charges (<0.3 e) should be interpreted with care. We use these validated charges to provide physical insight into nitrogen atomic charges for the ILs probed.
Publication Date: 21-May-2018
Date of Acceptance: 29-Dec-2017
URI: http://hdl.handle.net/10044/1/65385
DOI: https://dx.doi.org/10.1063/1.5011662
ISSN: 0021-9606
Publisher: AIP Publishing
Journal / Book Title: Journal of Chemical Physics
Volume: 148
Issue: 19
Copyright Statement: © 2017 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Journal of Chemical Physics 2018 148:19 and may be found at https://dx.doi.org/10.1063/1.5011662
Keywords: Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
RAY PHOTOELECTRON-SPECTROSCOPY
CATION-ANION INTERACTIONS
DENSITY-FUNCTIONAL THEORY
ELECTRONIC-STRUCTURE
ABSORPTION-SPECTROSCOPY
OXIDATION-STATE
IMIDAZOLIUM
ANALOGS
XPS
MOLECULES
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
RAY PHOTOELECTRON-SPECTROSCOPY
CATION-ANION INTERACTIONS
DENSITY-FUNCTIONAL THEORY
ELECTRONIC-STRUCTURE
ABSORPTION-SPECTROSCOPY
OXIDATION-STATE
IMIDAZOLIUM
ANALOGS
XPS
MOLECULES
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Chemical Physics
Publication Status: Published
Article Number: 193817
Open Access location: http://eprints.whiterose.ac.uk/125903/
Online Publication Date: 2018-02-07
Appears in Collections:Chemistry



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