Jump to main content
Jump to site search

Issue 8, 2017
Previous Article Next Article

Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(CO3)3]4− (An = U–Cm): the plutonium turn

Author affiliations

Abstract

Actinyl-tricarbonato anions [(AnO2)(CO3)3]4− (An = U–Cm) in various environments were investigated using theoretical approaches of quantum-mechanics, molecular-mechanics and cluster-models. Cations and solvent molecules in the 2nd coordination sphere affect the equatorial An←Oeq bonds more than the axial An[triple bond, length as m-dash]Oax bonds. Common actinide contraction is found for calculated and experimental axial bond lengths of 92U to 94Pu, though no longer for 94Pu to 96Cm. The tendency of U to Pu forming actinyl(VI) species dwindles away toward Cm, which already features the preferred AnIII/LnIII oxidation state of the later actinides and all lanthanides. The well known change from d-type to typical U–Pu–Cm type and then to f-type behavior is labeled as the plutonium turn, a phenomenon that is caused by f-orbital energy-decrease and f-orbital localization with increase of both nuclear charge and oxidation state, and a non-linear variation of effective f-electron population across the actinide series. Both orbital and configuration mixing and occupation of antibonding 5f type orbitals increase, weakening the AnOax bonds and reducing the highest possible oxidation states of the later actinides.

Graphical abstract: Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(CO3)3]4− (An = U–Cm): the plutonium turn

Back to tab navigation

Supplementary files

Publication details

The article was received on 14 Oct 2016, accepted on 18 Jan 2017 and first published on 26 Jan 2017


Article type: Paper
DOI: 10.1039/C6DT03953G
Citation: Dalton Trans., 2017,46, 2542-2550
  •   Request permissions

    Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(CO3)3]4− (An = U–Cm): the plutonium turn

    J. Liu, G. P. Chen, W. Huang, D. L. Clark, W. H. E. Schwarz and J. Li, Dalton Trans., 2017, 46, 2542
    DOI: 10.1039/C6DT03953G

Search articles by author

Spotlight

Advertisements