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Titel: Density Functional Theory Descriptors for Ionic Liquids and the Introduction of a Coulomb Correction
VerfasserIn: Philippi, Frederik
Quinten, Anna
Rauber, Daniel
Springborg, Michael
Hempelmann, Rolf
Sprache: Englisch
Titel: The Journal of Physical Chemistry. A
Bandnummer: 123
Heft: 19
Seiten: 4188-4200
Verlag/Plattform: American Chemical Society
Erscheinungsjahr: 2019
Freie Schlagwörter: Anions
Cations
Charge transfer
Salts
Solvents
DDC-Sachgruppe: 500 Naturwissenschaften
Dokumenttyp: Journalartikel / Zeitschriftenartikel
Abstract: As a result of continuing ionic liquid research, it becomes clearer that charge transfer in ionic liquids has a physical reality. In a recent publication, we demonstrated the utility of simple density functional theory descriptors to estimate charge transfer for a large number of ion combinations, which is possible because the ions are treated separately. A major disadvantage found was that the charge transfer was systematically overestimated. In this work, we introduce a correction to account for the losses in Coulomb attraction when charge is transferred from the anion to the cation. We find that accounting for these losses is important to describe charge transfer in ionic liquids appropriately. The advantage that the calculations can be performed separately on the individual, isolated ions is maintained. The corrected as well as the uncorrected charge transfer have been calculated for over 4000 cation−anion combinations at the R(O)B3LYP/6-311+G(2d,p)//RB3LYP/6-31+G(d,p) level of theory. With the correction, the absolute values for the charge transfer are no longer unrealistically high and agree well with other charge transfer estimates from the literature. In general, the cumulative nature of the Haven ratio is now correctly mirrored in the relationship between the corrected theoretical charge transfer and the experimental estimate from the Nernst−Einstein relation. Earlier findings on the similarities between ether-functionalized and nonfunctionalized ionic liquids are confirmed. However, we also observe inconsistencies when using the experimental charge transfer estimates together with the ionicity interpretation of the Haven ratio. These can be interpreted as a hint toward the latter premise being wrong.
DOI der Erstveröffentlichung: 10.1021/acs.jpca.9b01831
URL der Erstveröffentlichung: https://doi.org/10.1021/acs.jpca.9b01831
Link zu diesem Datensatz: urn:nbn:de:bsz:291--ds-392988
hdl:20.500.11880/35431
http://dx.doi.org/10.22028/D291-39298
ISSN: 1520-5215
1089-5639
Datum des Eintrags: 15-Mär-2023
Bezeichnung des in Beziehung stehenden Objekts: Supporting Information
In Beziehung stehendes Objekt: https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.9b01831/suppl_file/jp9b01831_si_001.pdf
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.9b01831/suppl_file/jp9b01831_si_002.pdf
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.9b01831/suppl_file/jp9b01831_si_003.pdf
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.9b01831/suppl_file/jp9b01831_si_004.zip
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.9b01831/suppl_file/jp9b01831_si_005.zip
https://pubs.acs.org/doi/suppl/10.1021/acs.jpca.9b01831/suppl_file/jp9b01831_si_006.xlsx
Fakultät: NT - Naturwissenschaftlich- Technische Fakultät
Fachrichtung: NT - Chemie
Professur: NT - Prof. Dr. Kaspar Hegetschweiler
NT - Prof. Dr. Christopher Kay
NT - Prof. Dr. Michael Springborg
Sammlung:SciDok - Der Wissenschaftsserver der Universität des Saarlandes

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