a b s t r a c tAll-electron density functional theory was used to investigate atomic oxygen adsorption on a gallium stabilized d-plutonium (1 1 1) surface. High symmetry on-surface and interstitial adsorption sites, along with local environment (as determined by the absence or presence of gallium) were explored. The calculations comprised full structural relaxations. Spin-orbit-coupling was also taken into account to assess the complexity of absorbate-substrate interactions. We observed that O adsorbate prefers to bind strongly to a gallium deficient environment, with the most stable site being the threefold hollow fcc site and associated chemisorption energy of À5.06 eV. The binding energies were least favored when gallium is a nearest neighbor to the O adsorbate, suggesting that the presence of gallium in a plutonium matrix tends to slow down the oxide layer growth. Although the oxygen coordination is the highest in the interstitial sites, the adsorption energy is less favored compared to on-surface adsorption, implying that the diffusion of oxygen from the surface layer into the subsurface layers is an activated process. The adsorption process induced non-trivial deformations of the surface. Additionally, some delocalization of the plutonium 5f and 6d partial electron density of states (PDOS) at the Fermi energy was observed. Further analysis in the PDOS indicated that gallium tends to suppress hybridization between the plutonium 5f and oxygen 2p orbitals, while the 6d orbitals hybridized with oxygen 2p orbitals.Published by Elsevier B.V.

All-electron density functional theory was used to investigate δ-plutonium (δ-Pu) alloyed with gallium (Ga) impurities at 3.125, 6.25, 9.375 atomic (at)% Ga concentrations. The results indicated that the lowest energy structure is anti-ferromagnetic, independent of the Ga concentration. At higher Ga concentrations (>3.125 at%), the position of the Ga atoms are separated by four nearest neighbor Pu-Pu shells. The results also showed that the lattice constant contracts with increasing Ga concentration, which is in agreement with experimental data. Furthermore with increasing Ga concentration, the face-centered-cubic structure becomes more stably coupled with increasing short-range disorder. The formation energies show that the alloying process is exothermic, with an energy range of -0.028 to -0.099 eV/atom. The analyses of the partial density of states indicated that the Pu-Ga interactions are dominated by Pu 6d and Ga 4p hybridizations, as well as Ga 4s-4p hybridizations. Finally, the computed formation energies for vacancy and hydrogen-vacancy complexes within the 3.125 at% Ga cell were 1.12 eV (endothermic) and -3.88 eV (exothermic), respectively. In addition, the hydrogen atom prefers to interact much more strongly to the Pu atom than the Ga atom in the hydrogen-vacancy complex.

We employ density functional theory to explore the effects of impurities in the fluorite crystal structure of PuO2. The impurities that were considered are known impurities that exist in metallic δ-phase Pu, including H, C, Fe, and Ga. These impurities were placed at various high-symmetry sites within the PuO2 structure including an octahedral interstitial site, an interstitial site with coordination to two neighboring O atoms, an O substitutional site, and a Pu substitutional site. Incorporation energies were calculated to be energetically unfavorable for all sites except the Pu substitutional site. When impurities were placed in a Pu substitutional site, complexes incorporating the impurities and O formed within the PuO2 structure. The observed defect-oxygen structures were OH, CO3, FeO5, and GaO3. The presence of these defects led to distortion of the surrounding O atoms within the structure, producing long-range disorder of O atoms. In contrast, perturbations of Pu atoms had a relatively short-range effect on the relaxed structures. These effects are demonstrated via radial distribution functions for O and Pu vacancies. Calculated electronic structure revealed hybridization of the impurity atom with the O valence states and a relative decrease in the Pu 5f states. Minor differences in band gaps were observed for the defected PuO2 structures containing H, C, and Ga. Fe-containing structures, however, were calculated to have a significantly decreased band gap, where the implementation of a Hubbard U parameter on the Fe 3d orbitals will maintain the calculated PuO2 band gap.

Experimental measurements and theoretical evaluation of changes in chemical speciation of α-UO3 using XRD, EXAFS, TGA, and DFT calculations.

Density functional theory calculations have been performed to provide details of the structural and charge-transfer details related to the solid solution of hydrogen in (δ)-plutonium. We follow the Flanagan model that outlines the process by which hydrogen interacts with a metal to produce hydride phases, via a sequence of surface, interstitial and defect-bound (trapped) states. Due to the complexities of the electronic structure in plutonium solid-state systems, we take the pragmatic approach of adopting the 'special quasirandom structure' to disperse the atomic magnetic moments. We find that this approach produces sound structural and thermodynamic properties in agreement with the available experimental data. In δ-Pu, hydrogen has an exothermic binding energy to all of the states relevant in the Flanagan model, and, furthermore, is anionic in all these states. The charge transfer is maximized (i.e. most negative for hydrogen) in the hydride phase. The pathway from surface to hydride is sequentially exothermic, in the order surface < interstitial < grain boundary < vacancy < hydride (hydride being the most exothermic state). Thus, we find that there is no intermediate state that involves an endothermic increase in energy, consistent with the general experimental observations that the hydriding reaction in plutonium metal can proceed with zero apparent activation barrier.