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dc.contributor.authorGhosh, Abhik
dc.contributor.authorConradie, Jeanet
dc.date.accessioned2023-08-31T08:34:57Z
dc.date.available2023-08-31T08:34:57Z
dc.date.issued2023-01-25
dc.description.abstractQuantum chemical calculations have for some time predicted that perfluorinated polyhedral organic molecules should exhibit a low-energy LUMO consisting of the overlapping inward-pointing lobes of the C−F σ* orbitals. Accordingly, these molecules should be able to encapsulate an electron within the interior of their cavities. Inspired by the recent confirmation of this prediction for perfluorocubane, we have sought to identify additional perfluorinated cage molecules capable of this remarkable behavior, which we refer to as the perfluoro cage effect (PCE). Using DFT calculations with multiple well-tested exchange-correlation functionals and large STO-QZ4P basis sets, we have identified several systems including [n]prismanes (n = 3−6), [n]asteranes (n = 3−5), twistane, and two norbornadiene dimer cages that clearly exhibit the PCE. In other words, they exhibit a low-energy LUMO belonging to the total symmetric irreducible representation of the point group in question and adiabatic electron affinities ranging from somewhat under 1 eV to over 2 eV. A pronounced size effect appears to hold, with larger cages exhibiting higher electron affinities (EAs). The largest adiabatic EAs, well over 3 eV, are predicted for perfluorinated dodecahedrane and C<sub>60</sub>. In contrast, the PCE is barely discernible for perfluorinated tetrahedrane and bicyclo[1.1.1]pentane.en_US
dc.identifier.citationGhosh, Conradie. The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules. ACS Omega. 2023;8(5):4972-4975en_US
dc.identifier.cristinIDFRIDAID 2125396
dc.identifier.doi10.1021/acsomega.2c07374
dc.identifier.issn2470-1343
dc.identifier.urihttps://hdl.handle.net/10037/30575
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalACS Omega
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2023 The Author(s)en_US
dc.rights.urihttps://creativecommons.org/licenses/by/4.0en_US
dc.rightsAttribution 4.0 International (CC BY 4.0)en_US
dc.titleThe Perfluoro Cage Effect: A Search for Electron-Encapsulating Moleculesen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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Attribution 4.0 International (CC BY 4.0)
Except where otherwise noted, this item's license is described as Attribution 4.0 International (CC BY 4.0)