Photoluminescence of uranium(VI): quenching mechanism and role of uranium(V).

13:51 EDT 1st April 2015 | BioPortfolio

Summary of "Photoluminescence of uranium(VI): quenching mechanism and role of uranium(V)."

The photoluminescence of uranium(VI) is observed typically in the wavelength range 400-650 nm with the lifetime of several hundreds mus and is known to be quenched in the presence of various halide ions (case A) or alcohols (case B). Here, we show by density functional theory (DFT) calculations that the quenching involves an intermediate triplet excited state that exhibits uranium(V) character. The DFT results are consistent with previous experimental findings suggesting the presence of photoexcited uranium(V) radical pair during the quenching process. In the ground state of uranyl(VI) halides, the ligand contributions to the highest occupied molecular orbitals increase with the atomic number (Z) of halide ion allowing larger ligand-to-metal charge transfer (LMCT) between uranium and the halide ion. Consequently, a larger quenching effect is expected as Z increases. The quenching mechanism is essentially the same in cases A and B, and is driven by an electron transfer from the quencher to the UO(2)(2+) entity. The relative energetic stabilities of the triplet excited state define the "fate" of uranium, so that in case A uranium(V) is oxidized back to uranium(VI), while in case B uranium remains as pentavalent.


Institute of Radiochemistry, Forschungszentrum Dresden-Rossendorf (FZD), Bautzner Landstrasse 400, Dresden, 01328 Germany.

Journal Details

This article was published in the following journal.

Name: Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Pages: 8029-33


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Inorganic compounds that contain uranium as an integral part of the molecule.

Uranium. A radioactive element of the actinide series of metals. It has an atomic symbol U, atomic number 92, and atomic weight 238.03. U-235 is used as the fissionable fuel in nuclear weapons and as fuel in nuclear power reactors.

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Nuclear reaction in which the nucleus of a heavy atom such as uranium or plutonium is split into two approximately equal parts by a neutron, charged particle, or photon.

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