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Comparison of the Performances of Different Computational Methods to Calculate the Electrochemical Stability of Selected Ionic Liquids
- Source :
- Materials, Volume 14, Issue 12, Materials, Vol 14, Iss 3221, p 3221 (2021), Materials (Basel) 14 (2021): 3221-1–3221-12. doi:10.3390/ma14123221, info:cnr-pdr/source/autori:Paolone A.; Brutti S./titolo:Comparison of the performances of different computational methods to calculate the electrochemical stability of selected ionic liquids/doi:10.3390%2Fma14123221/rivista:Materials (Basel)/anno:2021/pagina_da:3221-1/pagina_a:3221-12/intervallo_pagine:3221-1–3221-12/volume:14
- Publication Year :
- 2021
- Publisher :
- Multidisciplinary Digital Publishing Institute, 2021.
-
Abstract
- The electrochemical stability windows (ESW) of selected ionic liquids have been calculated by comparing different computational approaches previously suggested in the literature. The molecular systems under study are based on di-alkyl imidazolium and tetra-alkyl ammonium cations coupled with two different imide anions (namely, bis-fluorosulfonyl imide and bis-trifluoromethyl sulfonyl imide), for which an experimental investigation of the ESW is available. Thermodynamic oxidation and reduction potentials have here been estimated by different models based on calculations either on single ions or on ionic couples. Various Density Functional Theory (DFT) functionals (MP2, B3LYP, B3LYP including a polarizable medium and empirical dispersion forces) were exploited. Both vertical and adiabatic transitions between the starting states and the oxidized or reduced states were considered. The approach based on calculations on ionic couples is not able to reproduce the experimental data, whatever the used DFT functional. The best quantitative agreement is obtained by calculations on single ions when the MP2 functional in vacuum is considered and the transitions between differently charged states are vertical (purely electronic without the relaxation of the structure). The B3LYP functional underestimates the ESW. The inclusion of a polar medium excessively widens the ESW, while a large shrinkage of the ESW is obtained by adopting an adiabatic transition scheme instead of a vertical transition one.
- Subjects :
- Technology
Materials science
Ionic bonding
Thermodynamics
02 engineering and technology
Electronic structure
Density functional theory
Electrochemical stability window
Imide anions
Ionic liquids
010402 general chemistry
01 natural sciences
London dispersion force
Article
Ion
ionic liquids
chemistry.chemical_compound
Polarizability
Physics::Atomic and Molecular Clusters
General Materials Science
Physics::Chemical Physics
Adiabatic process
density functional theory
Microscopy
QC120-168.85
QH201-278.5
021001 nanoscience & nanotechnology
Engineering (General). Civil engineering (General)
electronic structure
0104 chemical sciences
TK1-9971
chemistry
Descriptive and experimental mechanics
Ionic liquid
electrochemical stability window
imide anions
Electrical engineering. Electronics. Nuclear engineering
TA1-2040
0210 nano-technology
Subjects
Details
- Language :
- English
- ISSN :
- 19961944
- Database :
- OpenAIRE
- Journal :
- Materials
- Accession number :
- edsair.doi.dedup.....2430dd8ab42bab42a1e38af5c312e6b4
- Full Text :
- https://doi.org/10.3390/ma14123221