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At least 1,657 records · Page 92

Ion solvation as a predictor of lanthanide adsorption structures and energetics in alumina nanopores

Adsorption reactions at solid-water interfaces define elemental fate and transport and enable contaminant clean-up, water purification, and chemical separations. For nanoparticles and nanopores, nanoconfinement may lead to unexpected and hard-to-predict products and energetics of adsorption, compared to analogous unconfined surfaces. Here we use X-ray absorption fine structure spectroscopy and operando flow microcalorimetry to determine nanoconfinement effects on the energetics and local coordination environment of trivalent lanthanides adsorbed on Al 2 O 3 surfaces. We show that the nanoconfinement effects on adsorption become more pronounced as the hydration free energy, ΔG hydr , of a lanthanide decreases. Neodymium (Nd 3+ ) has the least exothermic ΔG hydr (-3336 kJ·mol -1 ) and forms mostly outer-sphere complexes on unconfined Al 2 O 3 surfaces but shifts to inner-sphere complexes within the 4 nm Al 2 O 3 pores. Lutetium (Lu 3+ ) has the most exothermic ΔG hydr (-3589 kJ·mol -1 ) and forms inner-sphere adsorption complexes regardless of whether Al 2 O 3 surfaces are nanoconfined. Importantly, the energetics of adsorption is exothermic in nanopores only, and becomes endothermic with increasing surface coverage. Changes to the energetics and products of adsorption in nanopores are ion-specific, even within chemically similar trivalent lanthanide series, and can be predicted by considering the hydration energies of adsorbing ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion-specific clustering of metal-amphiphile complexes in rare earth separations

The nanoscale structure of a complex fluid can play a major role in the selective adsorption of ions at the nanometric interfaces, which is crucial in industrial and technological applications. Here we study the effect of anions and lanthanide ions on the nanoscale structure of a complex fluid formed by metal-amphiphile complexes, using small angle X-ray scattering. The nano- and mesoscale structures we observed can be directly connected to the preferential transfer of light (La and Nd) or heavy (Er and Lu) lanthanides into the complex fluid from an aqueous solution. While toluene-based complex fluids containing trioctylmethylammonium-nitrate (TOMA-nitrate) always show the same mesoscale hierarchical structure regardless of lanthanide loading and prefer light lanthanides, those containing TOMA-thiocyanate show an evolution of the mesoscale structure as a function of the lanthanide loading and prefer heavy lanthanides. The hierarchical structure indicates the presence of attractive interactions between ion-amphiphile aggregates, causing them to form clusters. A clustering model that accounts for the hard sphere repulsions and short-range attractions between the aggregates has been adapted to model the X-ray scattering results. The new model successfully describes the nanoscale structure and helps in understanding the mechanisms responsible for amphiphile assisted ion transport between immiscible liquids. Accordingly, our results imply different mechanisms of lanthanide transport depending on the anion present in the complex fluid and correspond with anion-dependent trends in rare earth separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting and accessing metastable phases

Metastable phase formation of Ln 2 O 3 phases was explained and successfully predicted using calculated metastable phase diagrams. Irradiation experiments of Lu 2 O 3 show formation of 3 phases, confirming the prediction, showing a unique behavior.

36 MATERIALS SCIENCE↗

Synthesis, crystal and electronic structures, linear and nonlinear optical properties, and photocurrent response of oxyhalides CeHaVIO 4 (Ha = Cl, Br; VI = Mo, W)

Four heteroanionic oxyhalides, CeClMoO 4 , CeBrMoO 4 , CeClWO 4 , and CeBrWO 4 , have been studied as multifunctional materials, which show a combination of good second harmonic generation (SHG) response and photocurrent signals. Millimeter-sized CeHaVIO 4 (Ha = Cl, Br; VI = Mo, W) crystals were grown by halide salt flux. The crystal structure of CeHaVIO 4 crystals was accurately determined by single-crystal X-ray diffraction. CeClMoO 4 , CeBrMoO 4 , and CeBrWO 4 are isostructural to each other, and crystallize in the acentric LaBrMoO 4 structure type. CeClWO 4 crystallizes in a new structure type with unit cell parameters of a = 19.6059(2) Å, b = 5.89450(10) Å, c = 7.80090(10) Å, and β = 101.4746(8)°. The bandgaps of CeHaVIO 4 fall into the range of 2.8(1)–3.1(1) eV, which are much smaller than those of isotypic LaHaVIO 4 (Ha = Cl, Br; VI = Mo, W) in the range of 3.9(1)–4.3(1) eV. The narrowing of bandgaps in CeHaVIO 4 originates from the presence of partially filled 4f orbitals of cerium atoms, which was confirmed by density functional theory (DFT) calculations. The moderate bandgaps make CeHaVIO 4 suitable for infrared nonlinear optical (IR NLO) applications. CeBrMoO 4 and CeBrWO 4 exhibit moderate SHG responses of 0.58× AGS and 0.46× AGS, respectively, and are both type-I phase-matching materials. Moderate SHG response, easy growth of crystals, high ambient stability, and type-I phase-matching behavior make CeBrMoO 4 and CeBrWO 4 great materials for IR NLO applications. CeHaVIO 4 films also exhibited good photocurrent response upon light radiation. Furthermore, this work demonstrates the rich structural chemistry of the REHaVIO 4 (RE = Y, La–Lu; Ha = Cl, Br; VI = Mo, W) family and the potential presence of more multifunctional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of f -element complexation on the radiolysis of 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])

A systematic study of the impact on the chemical reactivity of the oxidising n-dodecane radical cation (RH˙ + ) with f-element complexed 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) has been undertaken utilizing time-resolved electron pulse radiolysis/transient absorption spectroscopy and high-level quantum mechanical calculations. Lanthanide ion complexed species, [Ln((HEH[EHP]) 2 ) 3 ], exhibited vastly increased reactivity (over 10× faster) in comparison to the non-complexed ligand in n-dodecane solvent, whose rate coefficient was k = (4.66 ± 0.22) × 10 9 M -1 s -1 . Similar reactivity enhancement was also observed for the corresponding americium ion complex, k = (5.58 ± 0.30) × 10 10 M -1 s -1 . The vastly increased reactivity of these f-element complexes was not due to simple increased diffusion-control of these reactions; rather, enhanced hole transfer mechanisms for the complexes were calculated to become energetically more favourable. Interestingly, the observed reactivity trend with lanthanide ion size was not linear; instead, the rate coefficients showed an initial increase (Lu to Yb) followed by a decrease (Tm to Ho), followed by another increase (Dy to La). This behaviour was excellently predicted by the calculated reaction volumes of these complexes. In conclusion, complementary cobalt-60 gamma irradiations for select lanthanide complexes demonstrated that the measured kinetic differences translated to increased ligand degradation at steady-state timescales, affording ~38% increase in ligand loss of a 1:1 [La((HEH[EHP]) 2 ) 3 ]: HEH[EHP] ratio system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Raman spectroscopic study of anhydrous and hydrous REE phosphates, oxides, and hydroxides

Rare earth elements (REE) include the lanthanides (La–Lu), Y, and Sc which are critical elements for the green energy transition. The REE show a decrease in ionic radii with increased atomic numbers, which results in a so-called lanthanide contraction systematically affecting crystal structures and mineral properties. Here we present a compilation of reference Raman spectra of ten REE sesquioxides (A-, B- and C-type), five REE hydroxides, eight xenotime-structured REE phosphate endmembers and two solid solutions, seven monazite-structured REE phosphate endmembers and two solid solutions and seven rhabdophane endmembers with up to five Ce 1–x LREE x rhabdophane solid solutions (LREE = La–Gd). Raman mode assignment is based on a detailed literature review summarizing existing analytical work and theoretical calculations and systematic trends observed in this study by analyzing different REE-bearing solids. Here, the wavenumbers of the main REE-O Raman band systematically increase with decreasing ionic radii forming discrete linear trends within isostructural mineral groups, that can be used to estimate the REE-O mode in other solids with known REE-O coordination numbers. Photoluminescence using 266 nm, 532 nm and 633 nm excitation laser wavelengths for REE-bearing oxides, hydroxides, anhydrous and hydrous phosphates is also presented providing a new framework for identifying REE-phases in phosphate-bearing natural mineral deposits.

58 GEOSCIENCES↗

A comprehensive approach for elucidating the interplay between 4f n +1 and 4f n 5d 1 configurations in Ln 2+ complexes

Lanthanides (Ln) are typically found in the +3 oxidation state. However, in recent decades, their chemistry has been expanded to include the less stable +2 oxidation state across the entire series except promethium (Pm), facilitated by the coordination of ligands such as trimethylsilylcyclopentadienyl, C 5 H 4 SiMe 3 (Cp'). The [LnCp' 3 ] complexes have been the workhorse for the synthesis and theoretical study of the fundamental aspects of divalent lanthanide chemistry, where experimental and computational evidence have suggested the existence of different ground state (GS) configurations, 4f n+1 or 4f n 5d 1 , depending on the specific metal. Standard reduction potentials and 4f n+1 to 4f n 5d 1 promotion energies have been two factors usually considered to rationalize the occurrence of these variable GS configurations, however the driving force behind this phenomenon is still not clear. In this work we present a comprehensive theoretical approach to shed light on this matter using the [LnCp 3 ] - model systems. We begin by calculating 4f n+1 to 4f n 5d 1 promotion energies and successfully correlate them with existing experimental data. Furthermore, we analyze how changes in the GS charge distribution between the Ln ions, LnCp 3 and the reduced [LnCp 3 ] - complexes (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) correlate with experimental trends in redox potentials and the calculated promotion energies. For this purpose, a comprehensive theoretical work that includes relativistic ligand field density functional theory (LFDFT) and relativistic ab initio wavefunction methods was performed. This study will help the rational design of suitable environments to tune the different GS configurations as well as modulating the spectroscopic properties of new Ln 2+ complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of T - and ρ -dependent decay rates and new (n, γ ) cross-sections on the s process in low-mass asymptotic giant branch stars

Aims. We study the impact of nuclear input related to weak-decay rates and neutron-capture reactions on predictions for the slow neutron-capture process (s process) in asymptotic giant branch (AGB) stars. We provide the first database of surface abundances and stellar yields of the isotopes heavier than iron from the Monash models. Methods. We ran nucleosynthesis calculations with the Monash post-processing code for seven stellar structure evolution models of low-mass AGB stars with three different sets of nuclear inputs. The reference set has constant decay rates and represents the set used in the previous Monash publications. The second set contains the temperature and density dependence of β decays and electron captures based on the default rates of nuclear NETwork GENerator (NETGEN). In the third set, we further update 92 neutron-capture rates based on re-evaluated experimental cross sections from the ASTrophysical Rate and rAw data Library. We compare and discuss the predictions of the sets relative to each other in terms of isotopic surface abundances and total stellar yields. We also compare the results to isotopic ratios measured in presolar stardust silicon carbide (SiC) grains from AGB stars. Results. The new sets of models result in a ∼66% solar s-process contribution to the p-nucleus 152 Gd, confirming that this isotope is predominantly made by the s process. The nuclear input updates result in predictions for the 80 Kr/ 82 Kr ratio in the He intershell and surface 64 Ni/ 58 Ni, 94 Mo/ 96 Mo, and 137 Ba/ 136 Ba ratios that are more consistent with the corresponding ratios measured in stardust; however, the new predicted 138 Ba/ 136 Ba ratios are higher than the typical values of the SiC grains. The W isotopic anomalies are in agreement with data from the analyses of other meteoritic inclusions. We confirm that the production of 176 Lu and 205 Pb is affected by too large uncertainties in their decay rates from NETGEN.

79 ASTRONOMY AND ASTROPHYSICS↗

The R-Process Alliance: Hunting for gold in the near-UV spectrum of 2MASS J05383296–5904280

Over the past few years, the R-Process Alliance (RPA) has successfully carried out a search for stars that are highly enhanced in elements produced via the rapid neutron-capture (r-) process. In particular, the RPA has identified a number of relatively bright, highly r-process-enhanced (r-II) stars, suitable for observations with the Hubble Space Telescope (HST), facilitating abundance derivation of elements such as gold (Au) and cadmium (Cd). This paper presents the detailed abundances derived for the metal-poor ([Fe/H] = −2.55) highly r-process-enhanced ([Eu/Fe] = +1.29) r-II star 2MASS J05383296–5904280. One-dimensional local thermodynamic equilibrium (LTE) elemental abundances were derived via equivalent width and spectral synthesis using high-resolution high signal-to-noise near-UV HST/STIS and optical Magellan/MIKE spectra. Abundances were determined for 43 elements, including 26 neutron-capture elements. In particular, abundances of the rarely studied elements Nb, Mo, Cd, Lu, Os, Pt, and Au are derived from the HST spectrum. These results, combined with RPA near-UV observations of two additional r-II stars, increase the number of Cd abundances derived for r-process-enriched stars from seven to ten and Au abundances from four to seven. A large star-to-star scatter is detected for both of these elements, highlighting the need for more detections enabling further investigations, specifically into possible non-LTE effects.

chemically peculiar stars↗

Multicomponent Reactions Among Alkyl Isocyanides, sp Reactants, and sp 2 Carbon Cages

We explored the reactivity and substrate scope of the reactions among an alkyl isocyanide, an sp-hybridized reactant (i.e. alkyne or allene), and a carbon cage, as a new approach to functionalize fullerenes and metallofullerenes. Furthermore, this account summarizes the key findings in our recent published work, and some original data for the reaction involving an isocyanide, allenes, and metallofullerene Lu 3 N@C 80 .

36 MATERIALS SCIENCE↗

Gallium oxide semiconductor-based large volume ultrafast radiation hard spectroscopic scintillators

We report on the development of the first-ever inorganic radiation-hard moisture-insensitive large volume spectroscopic semiconductor-based scintillator with less than 2 ns decay time and light yields as high as 8000 ph/MeV. Despite extensive research into scintillator materials, the quest for an ideal scintillator combining ultrafast decay times (akin to BaF 2 and Yb-doped scintillators such as Lu 2 O 3 :Yb), high light yields (exceeding 2000 photons per MeV), spectroscopic capabilities, and exceptional radiation hardness remain unfulfilled. In this study, we demonstrate and report for the first time the viability of large-volume (up to 20 mm thickness) gallium oxide (β-Ga 2 O 3 ) semiconductor-based scintillators for applications requiring these properties. These β-Ga 2 O 3 scintillators were grown using the fast turnaround (~2 days) crucible-free optical float zone (FZ) technique. The high light yield and ultrafast decay time of these high-purity n-type semiconductors with free carrier concentration of 6 × 10 17 cm –3 are attributed to native defects, specifically oxygen vacancies (V O ) and gallium–oxygen vacancy pairs (V Ga –V O ), generated during optimized FZ growth. The ultrafast decay, along with high light yield, enables excellent timing resolution and high count rate detection for applications like time-of-flight positron emission tomography, physics experiments, and nuclear safety. The radiation hardness of these devices has been documented in a separate publication.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The internal structure and geodynamics of Mars inferred from a 4.2-Gyr zircon record

Combining U–Pb ages with Lu–Hf data in zircon provides insights into the magmatic history of rocky planets. The Northwest Africa (NWA) 7034/7533 meteorites are samples of the southern highlands of Mars containing zircon with ages as old as 4476.3 ± 0.9 Ma, interpreted to reflect reworking of the primordial Martian crust by impacts. We extracted a statistically significant zircon population (n= 57) from NWA 7533 that defines a temporal record spanning 4.2 Gyr. Ancient zircons record ages from 4485.5 ± 2.2 Ma to 4331.0 ± 1.4 Ma, defining a bimodal distribution with groupings at 4474 ± 10 Ma and 4442 ± 17 Ma. We interpret these to represent intense bombardment episodes at the planet’s surface, possibly triggered by the early migration of gas giant planets. The unradiogenic initial Hf-isotope composition of these zircons establishes that Mars’s igneous activity prior to ~4.3 Ga was limited to impact-related reworking of a chemically enriched, primordial crust. A group of younger detrital zircons record ages from 1548.0 ± 8.8 Ma to 299.5 ± 0.6 Ma. The only plausible sources for these grains are the temporally associated Elysium and Tharsis volcanic provinces that are the expressions of deep-seated mantle plumes. The chondritic-like Hf-isotope compositions of these zircons require the existence of a primitive and convecting mantle reservoir, indicating that Mars has been in a stagnant-lid tectonic regime for most of its history. Our results imply that zircon is ubiquitous on the Martian surface, providing a faithful record of the planet’s magmatic history.

58 GEOSCIENCES↗

Airborne Release Fractions from Surrogate Nuclear Waste Fires Containing Lanthanide Nitrates and Depleted Uranium Nitrate in 30% Tributyl Phosphate in Kerosene

Airborne contaminants from fires containing nuclear waste represent significant health hazards and shape the design and operation of nuclear facilities. Much of the data used to formulate DOE-HDBK-3010-94, “Airborne Release Fractions/Rates and Respirable Fractions for Nonreactor Nuclear Facilities,” from the U.S. Department of Energy, were taken over 40 years ago. The objectives of this study were to reproduce experiments from Pacific Northwest Laboratories conducted in June 1973 employing current aerosol measurement methods and instrumentation, develop an enhanced understanding of particulate formation and transport from fires containing nuclear waste, and provide modeling and experimental capabilities for updating current standards and practices in nuclear facilities. A special chamber was designed to conduct small fires containing 25 mL of flammable waste containing lutetium nitrate, ytterbium nitrate, or depleted uranium nitrate. Carbon soot aerosols showed aggregates of primary particles ranging from 20 to 60 nm in diameter. In scanning electron microscopy, ~200-nm spheroidal particles were also observed dispersed among the fractal aggregates. The 200-nm spherical particles were composed of metal phosphates. Airborne release fractions (ARFs) were characterized by leaching filter deposits and quantifying metal concentrations with mass spectrometry. The average mass-based ARF for 238 U experiments was 1.0 × 10 -3 with a standard deviation of 7.5 × 10 -4 . For the original experiments, DOE-HDBK-3010-94 states, “Uranium ARFs range from 2 × 10 -4 to 3 × 10 -3 , an uncertainty of approximately an order of magnitude.” Therefore, current measurements were consistent with DOE-HDBK-3010-94 values. ARF values for lutetium and ytterbium were approximately one to two orders of magnitude lower than 238 U. Furthermore, metal nitrate solubility may have varied with elemental composition and temperature, thereby affecting ARF values for uranium surrogates (Yb and Lu). In addition to ARF data, solution boiling temperatures and evaporation rates can also be deduced from experimental data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Computational discovery of two-dimensional rare-earth iodides: promising ferrovalley materials for valleytronics

Two-dimensional Ferrovalley materials with intrinsic valley polarization are rare but highly promising for valley-based nonvolatile random access memory and valley filter devices. These ferromagnetic materials exhibit valleys at or near the Fermi level with intrinsic magnetism. The strong coupling between magnetism and spin–orbit coupling induces intrinsic valley polarization. Using Kinetically Limited Minimization, an unconstrained crystal structure prediction algorithm, and prototype sampling based on first-principles calculations, we have discovered new Ferrovalley materials, rare-earth iodides RI 2 , where R is a rare-earth element belonging to Sc, Y, or La-Lu, and I is Iodine. The rare-earth iodides are layered and demonstrate either 2H, 1T, or 1T d phase as the ground state in bulk, analogous to transition metal dichalcogenides (TMDCs). The calculated exfoliation energy of monolayers (MLs) is comparable to that of graphene and TMDCs, suggesting possible experimental synthesis. The MLs in the 2H phase exhibit ferromagnetism due to unpaired electrons in d and f orbitals. Throughout the rare-earth series, d bands have valley polarization at K and $\overline{K}$ points in the Brillouin zone in the vicinity of the Fermi level. Large intrinsic valley polarization in the range of 15–143 meV without external stimuli is observed in these Ferrovalley materials, which can be enhanced further by applying an in-plane bi-axial strain. These valleys can selectively be probed and manipulated for information storage and processing, potentially offering superior performance beyond conventional electronics and spintronics. Here we further show that the 2H ferromagnetic phase of RI 2 MLs possesses non-zero Berry curvature and exhibits anomalous valley Hall effect with considerable anomalous Hall conductivity. Our work will incite exploratory synthesis of the predicted Ferrovalley materials and their application in valleytronics and beyond.

2D materials↗

Screening the complex biological behavior of late lanthanides through genome-wide interactions

Abstract Despite their similar physicochemical properties, recent studies have demonstrated that lanthanides can display different biological behaviors. Hence, the lanthanide series can be divided into three parts, namely early, mid, and late lanthanides, based on their interactions with biological systems. In particular, the late lanthanides demonstrate distinct, but poorly understood biological activity. In the current study, we employed genome-wide functional screening to help understand biological effects of exposure to Yb(III) and Lu(III), which were selected as representatives of the late lanthanides. As a model organism, we used Saccharomyces cerevisiae, since it shares many biological functions with humans. Analysis of the functional screening results indicated toxicity of late lanthanides is consistent with disruption of vesicle-mediated transport, and further supported a role for calcium transport processes and mitophagy in mitigating toxicity. Unexpectedly, our analysis suggested that late lanthanides target proteins with SH3 domains, which may underlie the observed toxicity. This study provides fundamental insights into the unique biological chemistry of late lanthanides, which may help devise new avenues toward the development of decorporation strategies and bio-inspired separation processes.

Pallares, Roger M. (ORCID:0000000174238706)↗

Hybrid functional calculations of electronic structure and carrier densities in rare-earth monopnictides

The structural parameters and electronic structure of rare-earth pnictides are calculated using density functional theory (DFT) with the Heyd, Scuseria, and Ernzerhof (HSE06) screened hybrid functional. Specifically, we focus on RE-V compounds, with RE=La, Gd, Er, and Lu, and V=As, Sb, and Bi, and analyze the effects of spin-orbit coupling and treating the RE4$\textit{f}$ electrons as valence electrons in the projector augmented wave approach. The results of HSE06 calculations are compared with DFT within the generalized gradient approximation (DFT-GGA) and other previous calculations. We find that all these RE-V compounds are semimetals with electron pockets at the $\textit{X}$ point and hole pockets at Γ. Whereas in DFT-GGA the carrier density is significantly overestimated, the computed carrier densities using HSE06 is in good agreement with the available experimental data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Unravelling competing microscopic interactions at a phase boundary: A single-crystal study of the metastable antiferromagnetic pyrochlore Yb 2 Ge 2 O 7

We report inelastic neutron scattering measurements from our newly synthesized single crystals of the structurally metastable antiferromagnetic pyrochlore Yb 2 Ge 2 O 7 . We determine the four symmetry-allowed nearest-neighbor anisotropic exchange parameters via fits to linear spin wave theory supplemented by fits of the high-temperature specific heat using the numerical linked-cluster expansion method. The exchange parameters so-determined are strongly correlated to the values determined for the g-tensor components, as previously noted for the related Yb pyrochlore Yb 2 Ti 2 O 7 . To address this issue, we directly determined the g-tensor from electron paramagnetic resonance of 1% Yb-doped Lu 2 Ge 2 O 7 , thus enabling an unambiguous determination of the exchange parameters. Our results show that Yb 2 Ge 2 O 7 resides extremely close to the classical phase boundary between an antiferromagnetic Γ 5 phase and a splayed ferromagnet phase. By juxtaposing our results with recent ones on Yb 2 Ti 2 O 7 , our work illustrates that the Yb pyrochlore oxides represent ideal systems for studying quantum magnets in close proximity to classical phase boundaries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗