We report first-principles calculations of the phonon dispersion spectrum, thermal expansion, and heat capacity of uranium dioxide. The so-called direct method, based on the quasiharmonic approximation, is used to calculate the phonon frequencies within a density functional framework for the electronic structure. The phonon dispersions calculated at the theoretical equilibrium volume agree well with experimental dispersions. The computed phonon density of states (DOS) compare reasonably well with measurement data, as do also the calculated frequencies of the Raman and infrared active modes including the LO/TO splitting. To study the pressure dependence of the phonon frequencies we calculate phonon dispersions for several lattice constants. Our computed phonon spectra demonstrate the opening of a gap between the optical and acoustic modes induced by pressure. Taking into account the phonon contribution to the total free energy of UO2 its thermal expansion coefficient and heat capacity have been ab initio computed. Both quantities are in good agreement with available experimental data for temperatures up to about 500 K.
A computational study is presented of the structural, electronic, and magnetic properties of U 3 O 8 and Np 2 O 5 , which are actinide oxides in a higher oxidation state than the tetravalent state of the common dioxide phases, UO 2 and NpO 2 . The calculations are based on the density functional theory +U approach, in which additional Coulomb correlations on the actinide atom are taken into account. The calculated properties of these two higher oxidized actinide oxides are analyzed and compared to those of their tetravalent analogs. The optimized structural parameters of these noncubic oxides are found to be in reasonable agreement with available experimental data. U 3 O 8 is predicted to be a magnetic insulator, having one U atom in a hexavalent oxidation state and two U atoms in a pentavalent oxidation state. For Np 2 O 5 , which is also predicted to be an insulator, a complicated noncollinear magnetic structure is computed, leading to a nonzero overall magnetization with a slight antiferromagnetic canting. The calculated electronic structures are presented and the variation of the U 5f or Np 5f -O 2p hybridization with the oxidation state is analyzed. With increasing oxygen content, the nearly localized 5f electrons of the actinide elements are more positioned near the Fermi level and the hybridization between 5f and 2p states is markedly increased.
The electronic structure of single-crystal PuO 2 is studied using O 1s x-ray absorption (XA) and x-ray emission. Interpretation of the experimental data is supported by extensive first-principles calculations on the basis of the density functional theory + U approach. The measured XA spectra show a significant difference in intensity for the first two peaks between different spots or areas on the single crystal. Our theoretical simulations show that the first peak, at ∼531 eV, can be attributed to O 2p-Pu 5f hybridization, while the second peak, at ∼533.4 eV, is due to hybridization of O 2p with Pu d states. The reasons for the observed differences in the O 1s XA spectra are explored by calculating a number of defect structures PuO 2±x as well as by simulating the existence of Pu(V) sites. Our results indicate the presence of oxidation states higher than Pu(IV) in some areas of the single crystal. The findings also suggest that plutonium oxide with a Pu fraction in an oxidation state higher than Pu(IV) consists of inequivalent Pu sites with Pu (IV) O 2 and Pu (V) O 2 rather than representing a system where the Pu oxidation state is constantly fluctuating between Pu(IV) and Pu(V).
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