Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/10732
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dc.contributor.authorFormosinho, Sebastião J.-
dc.contributor.authorBurrows, Hugh D.-
dc.contributor.authorMiguel, Maria da Graça-
dc.contributor.authorAzenha, M. Emília D. G.-
dc.contributor.authorSaraiva, Isabel M.-
dc.contributor.authorRibeiro, A. Catarina D. N-
dc.contributor.authorKhudyakov, Igor V.-
dc.contributor.authorGasanov, Rashid G.-
dc.contributor.authorBolte, Michèle-
dc.contributor.authorSarakha, Mohamed-
dc.date.accessioned2009-07-17T15:34:22Z-
dc.date.available2009-07-17T15:34:22Z-
dc.date.issued2003-04-04-
dc.identifier.citationPhotochemical & Photobiological Sciences. 2 (2003) 569-575en_US
dc.identifier.issn1474-905X-
dc.identifier.urihttp://hdl.handle.net/10316/10732-
dc.description.abstractA detailed analysis of the photophysical behaviour of uranyl ion in aqueous solutions at room temperature is given using literature data, together with results of new experimental and theoretical studies to see whether the decay mechanism of the lowest excited state involves physical deactivation by energy transfer or a chemical process through hydrogen atom abstraction. Comparison of the radiative lifetimes determined from quantum yield and lifetime data with that obtained from the Einstein relationship strongly suggests that the emitting state is identical to that observed in the lowest energy absorption band. From study of the experimental rate and that calculated theoretically, from deuterium isotope effects and the activation energy for decay support is given to a deactivation mechanism of hydrogen abstraction involving water clusters to give uranium(V) and hydroxyl radicals. Support for hydroxyl radical formation comes from electron spin resonance spectra observed in the presence of the spin traps 5,5-dimethyl-1-pyrroline N-oxide and tert-butyl-N-phenylnitrone and from literature results on photoinduced uranyl oxygen exchange and photoconductivity. It has previously been suggested that the uranyl emission above pH 1.5 may involve an exciplex between excited uranyl ion and uranium(V). Evidence against this mechanism is given on the basis of quenching of uranyl luminescence by uranium(V), together with other kinetic reasoning. No overall photochemical reaction is observed on excitation of aqueous uranyl solutions, and it is suggested that this is mainly due to reoxidation of UO2+ by hydroxyl radicals in a radical pair. An alternative process involving oxidation by molecular oxygen is analysed experimentally and theoretically, and is suggested to be too slow to be a major reoxidation pathway.en_US
dc.language.isoengen_US
dc.publisherRoyal Society of Chemistryen_US
dc.rightsopenAccesseng
dc.titleDeactivation processes of the lowest excited state of [UO2(H2O)5]2+ in aqueous solutionen_US
dc.typearticleen_US
dc.identifier.doi10.1039/b300346a-
uc.controloAutoridadeSim-
item.grantfulltextopen-
item.languageiso639-1en-
item.fulltextCom Texto completo-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.deptFaculdade de Ciências e Tecnologia, Universidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.parentdeptUniversidade de Coimbra-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.researchunitCoimbra Chemistry Center-
crisitem.author.orcid0000-0001-6607-0026-
crisitem.author.orcid0000-0003-3127-2298-
crisitem.author.orcid0000-0002-1601-5501-
crisitem.author.orcid0000-0002-9495-2592-
Appears in Collections:FCTUC Química - Artigos em Revistas Internacionais
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