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Elemental and mixed actinide dioxides: An ab initio study

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Details

Original languageEnglish
Pages (from-to)611-629
Number of pages19
JournalJournal of Theoretical and Computational Chemistry
Volume11
Issue number3
DOIs
Publication statusPublished - Jun 2012
Publication typeA1 Journal article-refereed

Abstract

We present a systematic study of the electronic, geometric, and magnetic properties of the actinide dioxides, UO 2, PuO 2, AmO 2, U 0.5Pu 0.5O 2, U 0.5Am 0.5O 2 and Pu 0.5Am 0.5O 2. For UO 2, PuO 2 and AmO 2, both density functional and hybrid density functional theory (DFT and HDFT) have been used. The fractions of exact HartreeFock (HF) exchange chosen were 25% and 40% for the hybrid density functional. For U 0.5Pu 0.5O 2, U 0.5Am 0.5O 2 and Pu 0.5Am 0.5O 2, only HDFT with 40% exact HF exchange was used. Each compound has been studied at the nonmagnetic, ferromagnetic and anti-ferromagnetic configurations, with and without spinorbit coupling (SOC). The lattice parameters, magnetic structures, bulk moduli, band gaps and density of states have been computed and compared to available experimental data and other theoretical results. Pure DFT fails to provide a satisfactory qualitative description of the electronic and magnetic structures of the actinide dioxides. On the other hand, HDFT performs very well in the prediction and description of the properties of the actinide dioxides. Our total energy calculations clearly indicate that the ground-state structures are anti-ferromagnetic for all actinide dioxides considered here. The lattice constants and the band gaps expand with an increase of HF exchange in HDFT. The influence of SOC is found to be significant.

Keywords

  • Actinide dioxides, hybrid density functional theory, mixed actinide oxides