Structural, thermodynamic, electronic and elastic properties of Th 1-x U x O 2 and Th 1-x Pu x O 2 mixed oxides

• Published in: Physical chemistry chemical physics : PCCP 2020-03, Vol.22 (11), p.6406-6417
• Main Authors: Ghosh, P S, Arya, A
• Format: Article
• Language: English
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D0CP00220H

The structural, thermodynamic, electronic, and elastic properties of Th1-xUxO2 and Th1-xPuxO2 mixed oxides (MOX) have been calculated with Hubbard corrected density functional theory (DFT+U) to account for the strong 5f electron correlations. The ideal solid solution is approximated by special quasi-random structures and the U-ramping method is used to account for the presence of metastable states in the self-consistent field solution of the DFT+U approach. The mixing enthalpy (ΔHmix) is positive throughout the composition range of the Th1-xUxO2 MOX, consistent with a simple miscibility gap (at low temperature) phase diagram. The behavior of the Th1-xPuxO2 MOX is more complex, where ΔHmix is positive in the ThO2-rich region and negative in the PuO2-rich region. Electronic structure analysis shows that substitution of Th by U/Pu in ThO2 leads to a reduction of the average Th-O bond lengths, causing distortion in the crystal structure. The distortion in the crystal structure results in an increase in the conduction bandwidth and a reduction of the band-gap in the MOX. Good agreement of our DFT+U calculated elastic properties of ThO2, UO2 and PuO2 compounds with experiments leads to convincing prediction of these properties for Th1-xUxO2 and Th1-xPuxO2 MOX.