Polyradical Character and Spin Frustration in Fullerene Molecules: An Ab Initio Non-Collinear Hartree–Fock Study

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dc.citation.firstpage9925en_US
dc.citation.issueNumber42en_US
dc.citation.journalTitleThe Journal of Physical Chemistry Aen_US
dc.citation.lastpage9940en_US
dc.citation.volumeNumber118en_US
dc.contributor.authorJiménez-Hoyos, Carlos A.en_US
dc.contributor.authorRodríguez-Guzmán, R.en_US
dc.contributor.authorScuseria, Gustavo E.en_US
dc.contributor.orgChemistryen_US
dc.contributor.orgPhysics and Astronomyen_US
dc.date.accessioned2016-04-05T20:14:03Zen_US
dc.date.available2016-04-05T20:14:03Zen_US
dc.date.issued2014en_US
dc.description.abstractMost ab initio calculations on fullerene molecules have been carried out on the basis of the paradigm of the Hückel model. This is consistent with the restricted nature of the independent-particle model underlying such calculations, even in single-reference-based correlated approaches. Notwithstanding, previous works on some of these molecules using model Hamiltonians have clearly indicated the importance of short-range interatomic spin–spin correlations. In this work, we consider ab initio non-collinear Hartree–Fock (HF) solutions for representative fullerene systems: the bowl, cage, ring, and pentagon isomers of C20, and the larger C30, C36, C60, C70, and C84 fullerene cages. In all cases but the ring we find that the HF minimum corresponds to a truly non-collinear solution with a torsional spin density wave. Optimized geometries at the generalized HF (GHF) level lead to fully symmetric structures, even in those cases where Jahn–Teller distortions have been previously considered. The nature of the GHF solutions is consistent with the π-electron space becoming polyradical in nature: each p-orbital remains effectively singly occupied. The spin frustration, induced by the presence of pentagon rings on an otherwise antiferromagnetic background, is minimized at the HF level by aligning the spins with non-collinear arrangements. The long-range magnetic ordering observed is reminiscent of the character of broken symmetry HF solutions in polyacene systems.en_US
dc.identifier.citationJiménez-Hoyos, Carlos A., Rodríguez-Guzmán, R. and Scuseria, Gustavo E.. "Polyradical Character and Spin Frustration in Fullerene Molecules: An Ab Initio Non-Collinear Hartree–Fock Study." <i>The Journal of Physical Chemistry A,</i> 118, no. 42 (2014) American Chemical Society: 9925-9940. http://dx.doi.org/10.1021/jp508383z.en_US
dc.identifier.doihttp://dx.doi.org/10.1021/jp508383zen_US
dc.identifier.urihttps://hdl.handle.net/1911/88851en_US
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsThis is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.en_US
dc.rights.urihttp://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlen_US
dc.titlePolyradical Character and Spin Frustration in Fullerene Molecules: An Ab Initio Non-Collinear Hartree–Fock Studyen_US
dc.typeJournal articleen_US
dc.type.dcmiTexten_US
dc.type.publicationpublisher versionen_US
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