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doi:10.22028/D291-39298
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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