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Synthesis, Structural, and Electronic Properties of K4PuVIO2(CO3)3(cr): An Environmentally Relevant Plutonium
Ivan Pidchenko1,2, Juliane März2, Myrtille O J Y Hunault3
1Rossendorf Beamline at ESRF-The European Synchrotron, CS40220, 38043 Grenoble, Cedex 9, France.
Abstract:
The chemical properties of actinide materials are often predefined and described based on the data available for isostructural species. This is the case for potassium plutonyl (Pu) carbonate, K4PuVIO2(CO3)3(cr), a complex relevant for nuclear technology and the environment, of which the crystallographic and thermodynamic properties of which are still lacking. We report here the synthesis and characterization of Pu achieved by single-crystal X-ray diffraction analysis and high-energy-resolution fluorescence-detected X-ray absorption near-edge structure at the Pu M4-edge coupled with electronic structure calculations. The crystallographic properties of Pu are compared with isostructural uranium (U) and neptunium (Np) compounds. Actinyl (AnVI) axial bond lengths, [O-AnVI-O]2+, are correlated between solid, K4AnVIO2(CO3)3(cr), and aqueous, [AnVIO2(CO3)3]4-(aq) species for the U-Np-Pu series. The spectroscopic data are compared to KPuVO2CO3(cr) and PuIVO2(cr) to tackle the trend in the electronic structure of Pu regarding the oxidation state changes and local structural modifications around the Pu atom.
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