RESUMO
In actinide systems, the 5felectrons experience a uniquely delicate balance of effects and interactions having similar energy scales, which are often difficult to properly disentangle. This interplay of factors such as the dual nature of 5f-states, strong electronic correlations, and strong spin-orbit coupling results in electronically unusual and intriguing behavior such as multi-k antiferromagnetic ordering, multipolar ordering, Mott-physics, mixed valence configurations, and more. Despite the inherent allure of their exotic properties, the exploratory science of even the more basic, binary systems like the actinide oxides has been limited due to their toxicity, radioactivity, and reactivity. In this article, we provide an overview of the available synthesis techniques for selected binary actinide oxides, including the actinide dioxides, sesquioxides, and a selection of higher oxides. For these oxides, we also review and evaluate the current state of knowledge of their crystal structures and magnetic properties. In many aspects, substantial knowledge gaps exist in the current body of research on actinide oxides related to understanding their electronic ground states. Bridging these gaps is vital for improving not only a fundamental understanding of these systems but also of future nuclear technologies. To this end, we note the experimental techniques and necessary future investigations which may aid in better elucidating the nature of these fascinating systems.
RESUMO
Refining the anomalous dispersion parameters of the four uranium compounds NaUF5, NaU2F9, Cs2(UO2)TiO4, and Cs2(UO2)Ti2O6 gave insights into the crystallographic model improvement of very heavy atoms. We found that the values for the dispersive and absorptive parts, f' and fâ³, closely followed the X-ray absorption spectra on their L3, L2, and L1 edges. The obtained values are sensitive to the chemical environment at each crystallographically independent position. An incorrect treatment of the anomalous dispersion correction can lead to a wrong crystallographic model. The above-mentioned, already published structures were improved by this process. General guidelines were given for the crystal structure determination of very heavy compounds. When using Mo Kα radiation with uranium compounds, the proximity of its energy to the uranium L-edges causes a noticeable effect.
RESUMO
Neodymium is typically considered the best surrogate for trivalent americium and can be used to identify Am3+ containing materials that are likely to form. We have explored the alkaline-earth lanthanide borate phase space using alkaline-earth halide/carbonate fluxes. This resulted in the synthesis of new compounds AE5Ln(BO3)4X (AE = Ca, Sr; Ln = Pr, Nd, Eu, Tb; X = Cl, Br) and AE3Ln2(BO3)4 (AE = Sr, Ba; Ln = Pr, Nd) as well as the synthesis of two compounds of Ba8Ln2(BO3)6(B2O5) (Ln = Eu, Tb) crystallizing in a new structure type. Ba8Ln2(BO3)6(B2O5) crystallizes in the space group P21/n with lattice parameters a = 8.6002(3) Å, b = 7.9245(3) Å, c = 17.6697(7) Å, and ß = 91.3560(10)° for the Eu analogue, and the structure contains isolated LnO8 polyhedra connected into a framework by BO3 and B2O5 units. The fluorescence emission spectra of AE5Ln(BO3)4X (AE = Ca, Sr; Ln = Eu, Tb; X = Cl, Br) and Ba8Ln2(BO3)6(B2O5) (Ln = Eu, Tb) are reported.
RESUMO
We report on the detailed structural analysis of a series of 11 new quaternary rare earths containing thiosilicates, AkRE2Si2S8 (Ak = Ca and Sr; RE = La, Ce, Pr, Nd, Sm, Gd, and Tb), synthesized using the flux-assisted boron chalcogen mixture method. High quality crystals were grown and used to determine their crystal structures by single crystal X-ray diffraction. All members of the AkRE2Si2S8 series crystallize in the trigonal crystal system with space group R3Ì c (space group no. 167). Polycrystalline powders were used for physical property measurements, including magnetic susceptibility, diffuse reflectance in the UV-visible range, and scintillation. Magnetic measurements indicated that CaRE2Si2S8 (RE = Nd and Tb) exhibits paramagnetic behavior with a slightly negative Weiss constant. The band gaps of the materials were determined from diffuse reflectance data, and optical band gaps were estimated to be 2.5(1) and 2.9(1) eV for CaCe2Si2S8 and CaGd2Si2S8, respectively. CaCe2Si2S8, CaTb2Si2S8, and SrCe2Si2S8 exhibited intense green luminescence upon irradiation with 375 nm ultraviolet light and, furthermore, scintillated when exposed to X-rays. Radioluminescence measurements of CaCe2Si2S8 powder revealed green emission with an intensity approximately 14% of that emitted by bismuth germanium oxide powder.