ABSTRACT
The material presented herein focuses on the exploration of the production of gadolinium aluminum gallium garnet and lutetium oxyorthosilicate doped with cerium (GAGG:Ce and LSO:Ce, respectively) through mechanochemical means. Multiple parameters are explored including mass of starting material, ball size, rotational speed of the mill, number of balls employed, and material used for the milling container. Theoretical calculations were conducted using a pre-established equation and showed that, when all other parameters were held constant, in scenarios where (1) a smaller mass of sample, (2) faster revolutions per minute, (3) greater numbers of balls, or (4) a greater density of the material used for the vials and balls were employed, there should be higher energies imparted to the system. Actual results executed appeared to exhibit somewhat congruent results, but showed limitations due to experimental (non-idealized) conditions.
ABSTRACT
Knowledge-based design of extracting agents for selective binding of actinides is essential in stock-pile stewardship, environmental remediation, separations, and nuclear fuel disposal. Robust computational protocols are critical for in depth understanding of structural properties and to further advance the design of selective ligands. In particular, rapid radiochemical separations require predictive capabilities for binding in the gas phase. This study focuses on gas-phase binding preferences of cyclic imide dioximes to uranyl, neptunyl, plutonyl, and americyl. Structural properties, electron withdrawing effects, and their effects on binding preferences are studied with natural bond-order population analysis. The aromatic amidoximes are found to have a larger electron-donation effect than the aliphatic amidoximes. It is also found that plutonyl is more electron withdrawing than uranyl, neptunyl, and americyl when bound to the cyclic imide dioximes studied.
ABSTRACT
Efficient predictive capabilities are essential for the actinide series since regulatory constraints for radioactive work, associated costs needed for specialized facilities, and the short half-lives of many actinides present great challenges in laboratory settings. Improved predictive accuracy is advantageous for numerous applications including the optimization and design of separation agents for nuclear fuel and waste. One limitation of calculations in support of these applications is that the large variations observed from predictions obtained with currently available methods can make comparisons across studies uncertain. Benchmarking currently available computational methodologies is essential to establish reliable practices across the community to guarantee an accurate physical description of the systems studied. To understand the performance of a variety of common theoretical methods, a systematic analysis of differences observed in the prediction of structural characteristics, electron withdrawing effects, and binding energies of [An(NO3)]2+ (with An = Ac to Lr) in gas and aqueous phases is reported. Population analysis obtained with Mulliken and Löwdin reflect a large dependence on the level of theory of choice, whereas those obtained with natural bond orbital show larger consistency across methodologies. Predicted stability across the actinide series calculated with coupled cluster with perturbative doubles and triples at the triple ζ level is equivalent to the one obtained when extrapolated to the complete basis set limit. The ground state of [Fm(NO3)]2+ and [Md(NO3)]2+ is predicted to have an electronic structure corresponding to An III state in gas and An IV in aqueous phase, whereas the ground state of [An(NO3)]2+ (with An = Ac to Es, Lr) presents an electronic structure corresponding to An IV in the gas and aqueous phase. The compounds studied with No in gas and aqueous phase present a preferred No III state, and the Lr compounds did not follow trends predicted for the rest of the actinide series, as previously observed in studies regarding its unusual electronic structure relative to its position in the periodic table.
