Insight into the Crystal Structures and Physical Properties of the Uranium Borides UB1.78±0.02, UB3.61±0.041 and UB11.19±0.13

In this study we reported the synthesis of three polycrystalline uranium borides UB1.78±0.02, UB3.61±0.041, and UB11.19±0.13 and their analyses using chemical analysis, X-ray diffraction, SQUID magnetometry, solid-state NMR, and Fourier transformed infrared spectroscopy. We discuss the effects of stoichiometry deviations on the lattice parameters and magnetic properties. We also provide their static and MAS-NMR spectra showing the effects of the 5f-electrons on the 11B shifts. Finally, the FTIR measurements showed the presence of a local disorder.

A Comparative Study of Electron Radiation Responses of Pu2Zr2O7 and La2Zr2O7: An abinitio Molecular Dynamics Study

In this study, the response of Pu2Zr2O7 and La2Zr2O7 to electronic radiation is simulated, employing an ab initio molecular dynamics method. It is shown that Pu2Zr2O7 undergoes a crystalline-to-amorphous structural transition with 0.3% electronic excitation, while for La2Zr2O7, the structural amorphization occurs with 1.2% electronic excitation. During the microstructural evolution, the anion disorder further drives cation disorder and eventually results in the structural amorphization of Pu2Zr2O7 and La2Zr2O7. The difference in responses to electron radiation between Pu2Zr2O7 and La2Zr2O7 mainly results from the strong correlation effects between Pu 5f electrons and the smaller band gap of Pu2Zr2O7. These results suggest that Pu2Zr2O7 is less resistant to amorphization under local ionization rates that produce a low level of electronic excitation, since the level of the concentration of excited electrons is relatively low in Pu2Zr2O7. The presented results will advance the understanding of the radiation damage effects of zirconate pyrochlores.

Intermediate occupation numbers for 5f electrons in a Pu and U mixed oxide

In order to reveal correlation effect on the electronic properties in particular 5f occupation of Pu/U ions in a (Pu,U) mixed oxide-PuUO4, a first principles calculation is performed by using...

Thermodynamics of Plutonium Monocarbide from Anharmonic and Relativistic Theory

Thermodynamics of plutonium monocarbide is studied from first-principles theory that includes relativistic electronic structure and anharmonic lattice vibrations. Density-functional theory (DFT) is expanded to include orbital-orbital coupling in addition to the relativistic spin-orbit interaction for the electronic structure and it is combined with anharmonic, temperature dependent, lattice dynamics derived from the self-consistent ab initio lattice dynamics (SCAILD) method. The obtained thermodynamics are compared to results from simpler quasi-harmonic theory and experimental data. Formation enthalpy, specific heat, and Gibbs energy calculated from the anharmonic model are validated by direct comparison with a calculation of phase diagram (CALPHAD) assessment of PuC and sub-stochiometric PuC0.896. Overall, the theory reproduces CALPHAD results and measured data for PuC rather well, but the comparison is hampered by the sub-stoichiometric nature of plutonium monocarbide. It was found that a bare theoretical approach that ignores spin-orbit and orbital-orbital coupling (orbital polarization) of the plutonium 5f electrons promotes too soft phonons and Gibbs energies that are incompatible with that of the CALPHAD assessment of the experimental data. The investigation of PuC suggests that the electronic structure is accurately described by plutonium 5f electrons as “band like” and delocalized, but correlate through spin polarization, orbital polarization, and spin-orbit coupling, in analogy to previous findings for plutonium metal.

Towards the Quantification of 5f Delocalization

By using M4,5 X-ray Emission Spectroscopy (XES) in the tender X-ray regime, it is possible to quantify 5f delocalization in the actinides. Previous analyses, utilizing the Branching Ratio (BR) in the N4,5 X-ray Absorption Spectroscopy (XAS), could not discriminate between the cases of localized n = 2 and delocalized n = 3, in uranium materials, where n is the number of 5f electrons on the U entity. Here, it is shown that, by employing the ubiquitous 6p → 3d XES as a point of normalization, the localized n = 2 and delocalized n = 3 cases can be easily distinguished and quantified.

Origins of the odd optical observables in plutonium and americium tungstates

A series of f-block tungstates show atypical coloration for both the Ce(iii) and Pu(iii) compounds; whereas the other lanthanide and Am(iii) compounds possess normal absorption features. The different optical properties are actually derived from the tungstate component rather than from 5f electrons/orbitals.