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dc.contributor.authorMansikkamäki, Akseli
dc.contributor.authorPopov, Alexey A.
dc.contributor.authorDeng, Qingming
dc.contributor.authorIwahara, Naoya
dc.contributor.authorChibotaru, Liviu F.
dc.date.accessioned2017-10-24T10:11:25Z
dc.date.available2018-09-30T21:35:37Z
dc.date.issued2017
dc.identifier.citationMansikkamäki, A., Popov, A. A., Deng, Q., Iwahara, N., & Chibotaru, L. F. (2017). Interplay of spin-dependent delocalization and magnetic anisotropy in the ground and excited states of [Gd2@C78]− and [Gd2@C80]−. <i>Journal of Chemical Physics</i>, <i>147</i>(12), Article 124305. <a href="https://doi.org/10.1063/1.5004183" target="_blank">https://doi.org/10.1063/1.5004183</a>
dc.identifier.otherCONVID_27288953
dc.identifier.otherTUTKAID_75354
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/55681
dc.description.abstractThe magnetic properties and electronic structure of the ground and excited states of two recently characterized endohedral metallo-fullerenes, [Gd2@C78]− (1) and [Gd2@C80]− (2), have been studied by theoretical methods. The systems can be considered as [Gd2]5+ dimers encapsulated in a fullerene cage with the fifteen unpaired electrons ferromagnetically coupled into an S = 15/2 high-spin configuration in the ground state. The microscopic mechanisms governing the Gd–Gd interactions leading to the ferromagnetic ground state are examined by a combination of density functional and ab initio calculations and the full energy spectrum of the ground and lowest excited states is constructed by means of ab initio model Hamiltonians. The ground state is characterized by strong electron delocalization bordering on a σ type one-electron covalent bond and minor zero-field splitting (ZFS) that is successfully described as a second order spin-orbit coupling effect. We have shown that the observed ferromagnetic interaction originates from Hund’s rule coupling and not from the conventional double exchange mechanism. The calculated ZFS parameters of 1 and 2 in their optimized geometries are in qualitative agreement with experimental EPR results. The higher excited states display less electron delocalization, but at the same time they possess unquenched first-order angular momentum. This leads to strong spin-orbit coupling and highly anisotropic energy spectrum. The analysis of the excited states presented here constitutes the first detailed study of the effects of spin-dependent delocalization in the presence of first order orbital angular momentum and the obtained results can be applied to other mixed valence lanthanide systems.
dc.language.isoeng
dc.publisherAmerican Institute of Physics
dc.relation.ispartofseriesJournal of Chemical Physics
dc.subject.othermakromolekyylit
dc.subject.otherfullereenit
dc.subject.otherharvinaiset maametallit
dc.subject.othermagneettiset ominaisuudet
dc.subject.othermacromolecules
dc.subject.otherfullerenes
dc.subject.otherrare earth metals
dc.subject.othermagnetic properties
dc.titleInterplay of spin-dependent delocalization and magnetic anisotropy in the ground and excited states of [Gd2@C78]− and [Gd2@C80]−
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201710164004
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineNanoscience Centerfi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.contributor.oppiaineNanoscience Centeren
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2017-10-16T12:15:15Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.relation.issn0021-9606
dc.relation.numberinseries12
dc.relation.volume147
dc.type.versionpublishedVersion
dc.rights.copyright© 2017 AIP Publishing. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.relation.grantnumber282499
dc.subject.ysomagneettiset ominaisuudet
dc.subject.ysomakromolekyylit
dc.subject.ysoharvinaiset maametallit
dc.subject.ysofullereenit
jyx.subject.urihttp://www.yso.fi/onto/yso/p597
jyx.subject.urihttp://www.yso.fi/onto/yso/p139
jyx.subject.urihttp://www.yso.fi/onto/yso/p15798
jyx.subject.urihttp://www.yso.fi/onto/yso/p137
dc.relation.doi10.1063/1.5004183
dc.relation.funderSuomen Akatemiafi
dc.relation.funderResearch Council of Finlanden
jyx.fundingprogramAkatemiahanke, SAfi
jyx.fundingprogramAcademy Project, AoFen
jyx.fundinginformationWe would like thank Professor Tatsuhisa Kato (Kyoto University) for sending us his unpublished EPR data and for useful discussions. A.M. gratefully acknowledges computational resources provided by Professor H. M. Tuononen (University of Jyväskylä) and CSC-IT Center for Science, Ltd., in Finland as well as funding provided by the Academy of Finland (Project No. 282499). N.I. is a JSPS Overseas Research Fellow.
dc.type.okmA1


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