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dc.contributor.authorNetzsch, Philip
dc.contributor.authorHämmer, Matthias
dc.contributor.authorTurgunbajew, Erich
dc.contributor.authorvan Swieten, Thomas P.
dc.contributor.authorMeijerink, Andries
dc.contributor.authorHöppe, Henning A.
dc.contributor.authorSuta, Markus
dc.identifier.citationNetzsch , P , Hämmer , M , Turgunbajew , E , van Swieten , T P , Meijerink , A , Höppe , H A & Suta , M 2022 , ' Beyond the energy gap law : the influence of selection rules and host compound effects on nonradiative transition rates in boltzmann thermometers ' , Advanced Optical Materials , vol. 10 , no. 11 , 2200059 .
dc.identifier.otherPURE: 278822137
dc.identifier.otherPURE UUID: c285b09e-d916-4b6f-bfa8-ca90d1c43279
dc.identifier.otherRIS: urn:2DE249297BDDCE8C828270C50B0D199D
dc.identifier.otherScopus: 85127543629
dc.identifier.otherWOS: 000779118200001
dc.descriptionP.N. and M.H. contributed equally to this work. H.A.H., P.N., M.H., and E.T. thank the Deutsche Forschungsgemeinschaft (DFG) for generous support (Project HO 4503/5-1). Open access funding enabled and organized by Projekt DEAL.en
dc.description.abstractApart from the energy gap law, control parameters over nonradiative transitions are so far only scarcely regarded. In this work, the impact of both covalence of the lanthanoid–ligand bond and varying bond distance on the magnitude of the intrinsic nonradiative decay rate between the excited 6P5/2 and 6P7/2 spin–orbit levels of Gd3+ is investigated in the chemically related compounds Y2[B2(SO4)6] and LaBO3. Analysis of the temperature-dependent luminescence spectra reveals that the intrinsic nonradiative transition rates between the excited 6PJ (  J = 5/2, 7/2) levels are of the order of only 10 ms−1 (Y2[B2(SO4)6]:Gd3+: 8.9 ms−1; LaBO3:Gd3+: 10.5 ms−1) and differ due to the different degree of covalence of the Gd—O bonds in the two compounds. Comparison to the established luminescent Boltzmann thermometer Er3+ reveals, however, that the nonradiative transition rates between the excited levels of Gd3+ are over three orders of magnitude slower despite a similar energy gap and the presence of a single resonant phonon mode. This hints to a fundamental magnetic dipolar character of the nonradiative coupling in Gd3+. These findings can pave a way to control nonradiative transition rates and how to tune the dynamic range of luminescent Boltzmann thermometers.
dc.relation.ispartofAdvanced Optical Materialsen
dc.rightsCopyright © 2022 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.en
dc.subjectLuminescence thermometryen
dc.subjectNonradiative transitionsen
dc.subjectStructure–property relationshipen
dc.subjectQD Chemistryen
dc.titleBeyond the energy gap law : the influence of selection rules and host compound effects on nonradiative transition rates in boltzmann thermometersen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.description.statusPeer revieweden

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