Experimental validation of calculated atomic charges in ionic liquids

Fogarty, Richard M.; Matthews, Richard P.; Ashworth, Claire; Brandt-Talbot, Agnieszka; Palgrave, Robert G.; Bourne, Richard A.; Hoogerstraete, Tom Vander; Hunt, Patricia A.; Lovelock, Kevin R. J.

doi:10.1063/1.5011662

Cited by 30 publications

(27 citation statements)

References 79 publications

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“…Recently it was proposed that the BEs obtained from fitting the experimental XPS spectra for ILs correlate with the calculated atomic charges. [ 32,33 ] Figure 6 demonstrates a modest correlation between the BE approximated by the first and third terms of Equation ) (BE = V [ q i ]) and the calculated relative ΔKS BE values. The relation improves significantly by considering the effect of the electrostatic potential of neighboring atoms given by the second term in Equation ) (BE = V [ q i , q j ]).…”

Section: Resultsmentioning

confidence: 99%

“…[ 31 ] Fogarty et al found such correlation for the S 1s electrons ( R 2 = 0.98) and N 1s electrons ( R 2 = 0.94) between the experimental BEs and the computed atomic charges. [ 32,33 ] Kruusma et al calculated C 1s electrons' Kohn–Sham (KS) orbital energies and used their values for fitting the experimental spectra. [ 17 ] Similarly, Reinmöller et al used the KS orbital energies to calculate the BEs for the XPS spectra.…”

Section: Introductionmentioning

confidence: 99%

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Calculation of core‐level electron spectra of ionic liquids

Lembinen

Nõmmiste

Ers

et al. 2020

Int J of Quantum Chemistry

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On the example of 40 ion pairs (5 cations times 8 anions), this study demonstrates how the core-level binding energy values can be calculated and used to plot theoretical spectra at low computational cost using density functional theory methods. Three approaches for obtaining the binding energy values are based on delta Kohn-Sham (ΔKS) calculations, 1s KS orbital energies, and atomic charges. The ΔKS results show reasonable agreement with the available experimental X-ray photoelectron data. The 1s KS orbital energies correlate well with the ΔKS results. Atomic charge correlation with ΔKS is improved by accounting for the charges of neighboring atoms. Assignment of binding energies to atoms and the applicability of the mentioned methods to model systems of ionic liquids are discussed. K E Y W O R D S core-level binding energy, delta Kohn-Sham, Green function, ionic liquid, X-ray photoelectron spectra

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Calculation of core‐level electron spectra of ionic liquids

Lembinen

Nõmmiste

Ers

et al. 2020

Int J of Quantum Chemistry

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“…[43][44][45] The choice of the ChelpG method is based on the promising results reported by Lovelock and coworkers recently. 46 All of the input files are available in the Supporting Information (SI).…”

Section: Computational Detailsmentioning

confidence: 99%

“…Using this approach, it is possible to obtain a better charge description due to the use of different representative structures from the IL pairs and the oligomer conformations 43–45 . The choice of the ChelpG method is based on the promising results reported by Lovelock and coworkers recently 46 . All of the input files are available in the Supporting Information (SI).…”

Section: Computational Detailsmentioning

confidence: 99%

A molecular dynamics study of a fully zwitterionic copolymer/ionic liquid‐based electrolyte: Li⁺ transport mechanisms and ionic interactions

et al. 2021

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The development of polymer electrolytes (PEs) is crucial for advancing safe, high-energy density batteries, such as lithium-metal and other beyond lithium-ion chemistries. However, reaching the optimum balance between mechanical stiffness and ionic conductivity is not a straightforward task. Zwitterionic (ZI) gel electrolytes comprising lithium salt and ionic liquid (IL) solutions within a fully ZI polymer network can, in this context, provide useful properties. Although such materials have shown compatibility with lithium metal in batteries, several fundamental structure-dynamic relationships regarding ionic transport and the Li + coordination environment remain unclear. To better resolve such issues, molecular dynamics simulations were carried out for two IL-based electrolyte systems, N-butyl-N-methylpyrrolidinium

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“…shifts < 0.5 eV in IL XP spectra in terms of atomic charges. 32,37 Despite this, correlations between core-electron B.E.s and physicochemical properties (e.g. Kamlettaft parameters) 21,22,31 support the drive for accurate peak fittings, regardless of the physical interpretation of the data.…”

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confidence: 99%