Jump to main content
Jump to site search

Issue 2, 2015
Previous Article Next Article

Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation – a case study of uranyl(VI) hydrolysis

Author affiliations

Abstract

This study of aqueous metal speciation is an advanced combination of theoretical and experimental methods. Continuous wave (CW) and time-resolved laser-induced fluorescence spectroscopy (TRLFS) data of uranyl(VI) hydrolysis were analyzed using parallel factor analysis (PARAFAC). Distribution patterns of five major species were thereby derived under a fixed uranyl concentration (10−5 M) over a wide pH range from 2 to 11. UV (180 nm to 370 nm) excitation spectra were extracted for individual species. Time-dependent density functional theory (TD-DFT) calculations revealed ligand excitation (water, hydroxo, oxo) in this region and ligand-to-metal charge transfer (LMCT) responsible for luminescence. Thus excitation in the UV region is extreme ligand sensitive and specific. Combining findings from PARAFAC and DFT the [UO2(H2O)5]2+ cation (aquo complex 1 : 0) and four hydroxo complexes (1 : 1, 3 : 5, 3 : 7 and 1 : 3) were identified. The methodological concept used here is applicable to luminescent metals in general and thus enables acquisition of refined structural and thermodynamical data of lanthanide and actinide complexation.

Graphical abstract: Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation – a case study of uranyl(vi) hydrolysis

Back to tab navigation

Supplementary files

Publication details

The article was received on 08 Jul 2014, accepted on 24 Oct 2014 and first published on 28 Oct 2014


Article type: Edge Article
DOI: 10.1039/C4SC02022G
Citation: Chem. Sci., 2015,6, 964-972
  • Open access: Creative Commons BY-NC license
  •   Request permissions

    Combining luminescence spectroscopy, parallel factor analysis and quantum chemistry to reveal metal speciation – a case study of uranyl(VI) hydrolysis

    B. Drobot, R. Steudtner, J. Raff, G. Geipel, V. Brendler and S. Tsushima, Chem. Sci., 2015, 6, 964
    DOI: 10.1039/C4SC02022G

    This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements