Actinide 4f x-ray absorption in oxides
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Butorin, Sergei M.↗
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Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 – : Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4
The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3 (NO 3 ) 2 -, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 - . Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due to condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4 , which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf( II )
The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf II is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf II (CH 3 SO 2 ) 3 -, prepared in the gas phase by reductive elimination of CH 3 SO 2 from Cf III (CH 3 SO 2 ) 4 -. Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of CfIII and SmIII, and no evidence for reduction of Cm III . This reflects the comparative 3+/2+ reduction potentials: Cf 3+ (-1.60 V) ≈ Sm 3+ (-1.55 V) >> Cm 3+ (-3.7 V). Association of O 2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. Lastly, the new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf II coordination complexes and similar chemistry of Cf and Sm.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Role of dynamical effects in the formation of T-Odd asymmetries for products of polarized-neutron-induced ternary fission of nuclei
Basic dynamical effects that accompany the cold-polarized-neutron-induced binary and ternary fission of actinide nuclei and which determine the properties of T -odd asymmetries in angular distributions of various prescission and evaporated light third particles emitted in true and delayed ternary fission are analyzed on the basis of quantum-mechanical fission theory. It is emphasized that effects associated with the conservation of axial symmetry of the fissioning system under study at all stages of its evolution from the formation of neutron resonance states of the fissile compound nucleus to the separation of its fission fragments, including the appearance of zero wriggling vibrations of the cold compound nucleus in the vicinity of its scission point, are of particular importance, the influence of quantum collective rotation of the polarized fissile system on the asymmetry of the angular distribution of both fission fragments and third particles being taken into account. It is shown that the difference in the behavior of the coefficients characterizing the T -odd asymmetries under analysis for the target nuclei being studied can be explained, upon taking into account the interference between the fission amplitudes for the neutron resonance states of fissile compound nuclei, by the difference in the contributions of even and odd components of the amplitudes of angular distributions of third particles to the coefficients in question.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Synthesis of uranium mixed anion compounds synthesized using the Boron-Chalcogen Mixture method: Ba 6 Co 6 U 0·9 1S 13·5 O 0.5 and Ba 5·47 K 0·53 Zn 6 US 13·5 O 0.5
Mixed anion compounds have exhibited interesting structures and properties that differ from compounds only incorporating a single anion in their composition. Unfortunately, difficulties in the synthetic methods used to obtain these materials has slowed the evolution of this field, prompting investigations into alternate synthetic pathways to these materials. Our recently establish Boron-Chalcogen Mixture (BCM) method, which was originally developed for the synthesis of pure actinide chalcogenides from oxides, has been adapted to achieve the partial oxide to sulfide conversion of Ba 2 MUO 6 (M = Co, Zn) which resulted in two new uranium (IV/V) oxysulfide compounds, Ba 6 Co 6 U 0·91 S 13·5 O 0.5 and Ba 5·47 K 0·53 Zn 6 US 13·5 O 0.5 These compounds crystallize in the tetragonal crystal system adopting the space group I4/mcm. Finally, their syntheses, crystal structures, and trends observed in the pursuit of these new mixed anion compounds are reported.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Formation of Fully Stoichiometric, Oxidation-State Pure Neptunium and Plutonium Dioxides from Molecular Precursors
Amidate-based ligands (N-(tert-butyl)isobutyramide, ITA) bind κ 2 to form homoleptic, 8-coordinate complexes with tetravalent 237 Np (Np(ITA) 4 , 1-Np) and 242 Pu (Pu(ITA) 4 , 1-Pu). These compounds complete an isostructural series from Th, U–Pu and allow for the direct comparison between many of the early actinides with stable tetravalent oxidation states by nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction (SCXRD). The molecular precursors are subjected to controlled thermolysis under mild conditions with the exclusion of exogenous air and moisture, facilitating the removal of the volatile organic ligands and ligand byproducts. The preformed metal–oxygen bond in the precursor, as well as the metal oxidation state, are maintained through the decomposition, forming fully stoichiometric, oxidation-state pure NpO 2 and PuO 2 . Powder X-ray diffraction (PXRD), scanning transmission electron microscopy (STEM), and energy dispersive X-ray spectroscopy (EDS) elemental mapping supported the evaluation of these high-purity materials. This chemistry is applicable to a wide range of metals, including actinides, with accessible tetravalent oxidation states, and provides a consistent route to analytical standards of importance to the field of nuclear nonproliferation, forensics, and fundamental studies.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Structural and Bonding Analysis in Monomeric Actinide(IV) Oxalate from Th(IV) to Pu(IV): Comparison with the An(IV) Nitrate Series
In this work, single-crystal X-ray diffraction (SC-XRD) structures and Raman spectra of a series of new isomorphous molecular An(IV)-oxalate compounds (Th, U, Np, and Pu) are reported. These complexes are crystallized with cobalt(III) hexamine ([Co(NH 3 ) 6 ] 3+ ) as the counter cations, [Co(NH 3 ) 6 ] 2 [An(C 2 O 4 ) 5 ]·4H 2 O, revealing five bidentate nonbridging oxalate ligands in the first coordination sphere (CN = 10). The nonbridging oxalate is rather uncommon for An(IV)-oxalate systems, which are widely characterized as polymeric compounds. Density functional theory (DFT) calculations were performed to examine the bonding between An(IV) cations and oxalate ligands. For comparison, we also report results obtained for the An(IV)-hexanitrate series, [(C 2 H 5 ) 4 N] 2 [An(NO 3 ) 6 ] (with An = Th, U, Np, Pu, and Ce), which consists of O-donor ligands as well but with a larger coordination number (CN = 12). The bonding analysis confirms that the actinide–oxygen bond is predominantly ionic with a minor increase in covalency from Th to U and slight variations from U to Pu. Further comparison showed that the charge transfer increases slightly when increasing the number of anions in the coordination sphere (C 2 O$_4^{2–}$: CN = 10; NO$_3^–$: CN = 12), but covalent effects as indicated by the amount of internuclear electron density accumulation are small and similar for oxalate and nitrate.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
U(V) in metal uranates: a combined experimental and theoretical study of MgUO[subscript 4], CrUO[subscript 4], and FeUO[subscript 4]
Abstract not provided
Guo, Xiaofeng↗
R-matrix evaluation of the 15 N Compound System for Criticality Safety Analyses [Abstract]
The evaluation of the 15 N compound system was selected by the Nuclear Criticality Safety Program (NCSP) due to the importance of nitrogen in criticality benchmarks and in actinide chemistry encountered during fuel reprocessing. For improved accuracy in transport calculations, it is recommended to obtain and distribute resonance parameters to describe n + 14 N reactions.
AZURE↗
Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl–Organic Hybrid Materials
A series of compounds of the form [HAr]2[UO2X4] is reported here, wherein Ar is systematically varied between pyridine (1-X), quinoline (2-X), acridine (3-X), 2,5-dimethylpyrazine (4-X), quinoxaline (5-X), and phenazine (6-X), and X = Cl or Br. With greater conjugation in the organic cation, a larger quenching in uranyl luminescence is observed in the solid state. Supporting our luminescence experiments with computation, we map out the potential energy diagrams for the singlet and triplet states of both the [HAr]+ cations and [UO2Cl4]2– anion in the crystalline state, and of the assembly. The distinct energy transfer pathways in each compound are discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Unified Mechanism behind the Appearance of T-Odd TRI and ROT Asymmetries in Actinide Fission Induced by Cold Polarized Neutrons
Some shortcomings of the approaches that are used to describe T-odd ROT and TRI asymmetries in true ternary fission via reactions involving the emission of prescission alpha particles and which are based on employing the classical method of trajectory calculations are analyzed. These shortcomings are caused by the disregard of the interference between the fission widths of different sJ{sub s} neutron resonance states formed in the first well of the deformation potential of fissile compound nuclei. It is shown that the method used in some studies to determine T-odd TRI-asymmetries for prescission alpha particles is at odds with basic concepts of the generalizedmodel of the nucleus and approaches to constructing collective (for example, bending) vibrations of a fissile compound nucleus. Quantum-mechanical fission theory is generalized via employing a unified mechanism of formation of T-odd TRI and ROT asymmetries for prescission alpha particles and evaporated photons (neutrons). The proposed mechanism takes correctly into account the effect of quantum rotation of a fissile compound nucleus on the angular distributions of fission fragments and alpha particles for true ternary fission, as well as on the angular distribution of prompt photons (neutrons) emitted by fragments originating from the delayed fission of the aforementioned nuclei.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Facile Oxide to Chalcogenide Conversion for Actinides Using the Boron–Chalcogen Mixture Method
Actinide chalcogenides are of interest for fundamental studies of the behavior of 5f electrons in actinides located in a soft ligand coordination environment. As actinides exhibit an extremely high affinity for oxygen, the synthesis of phase pure actinide chalcogenide materials free of oxide impurities is a great challenge and, moreover, requires the availability and use of oxygen free starting materials. Herein, we report a new method, the Boron-Chalcogen Mixture (BCM) method, for the synthesis of phase pure uranium chalcogenides based on the use of a boron/chalcogen mixture, where boron functions as an “oxygen sponge” to remove oxygen from an oxide precursor and where the elemental chalcogen effects transformation of the oxide precursor into an oxygen free chalcogenide reagent. Here, the boron oxide can be separated from the reaction mixture that is left to react to form the desired chalcogenide product. Several syntheses are presented that demonstrate the broad functionali-ty of the technique and thermodynamic calculations that show the underlying driving force are discussed. Specifically, three classes of chalcogenides that include both new (rare earth uranium sulfides and alkali-thorium thiophosphates) and previously reported compounds were prepared to validate the approach: binary uranium and thorium sulfides, oxide to sulfide transfor-mation in solid state reactions, and in situ generation of actinide chalcogenides in flux crystal growth reactions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chelation and stabilization of berkelium in oxidation state +IV
Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here, in this work, we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin - a mammalian metal transporter - in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Finally, combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Machine learning molecular dynamics simulations toward exploration of high-temperature properties of nuclear fuel materials: case study of thorium dioxide
Predicting materials properties of nuclear fuel compounds is a challenging task in materials science. Their thermodynamical behaviors around and above the operational temperature are essential for the design of nuclear reactors. However, they are not easy to measure, because the target temperature range is too high to perform various standard experiments safely and accurately. Moreover, theoretical methods such as first-principles calculations also suffer from the computational limitations in calculating thermodynamical properties due to their high calculation-costs and complicated electronic structures stemming from f-orbital occupations of valence electrons in actinide elements. Here, we demonstrate, for the first time, machine-learning molecular-dynamics to theoretically explore high-temperature thermodynamical properties of a nuclear fuel material, thorium dioxide. The target compound satisfies first-principles calculation accuracy because f-electron occupation coincidentally diminishes and the scheme meets sampling sufficiency because it works at the computational cost of classical molecular-dynamics levels. We prepare a set of training data using first-principles molecular dynamics with small number of atoms, which cannot directly evaluate thermodynamical properties but captures essential atomistic dynamics at the high temperature range. Then, we construct a machine-learning molecular-dynamics potential and carry out large-scale molecular-dynamics calculations. Consequently, we successfully access two kinds of thermodynamic phase transitions, namely the melting and the anomalous λ transition induced by large diffusions of oxygen atoms. Furthermore, we quantitatively reproduce various experimental data in the best agreement manner by selecting a density functional scheme known as SCAN. Our results suggest that the present scale-up simulation-scheme using machine-learning techniques opens up a new pathway on theoretical studies of not only nuclear fuel compounds, but also a variety of similar materials that contain both heavy and light elements, like thorium dioxide.
74 ATOMIC AND MOLECULAR PHYSICS↗
Thermochemical modeling of the U1-yGdyO2 x phase
A thermodynamic model for the U1-yGdyO2 x phase was developed using the compound energy formalism (CEF) with a three sublattice approach and is an extension of the already successful CEF representation of the fluorite UO2 x phase. The Gibbs energies for the end-members created by the addition of Gd to the cation sublattice are estimated using the lattice stability of a fictive gadolinium oxide fluorite structure compound from density functional theory. The model interaction parameters are determined from reported oxygen potential-temperature-composition measurements. The calculated results are in good agreement with the experimental data and the trends are consistent. The CEF for the U1-yGdyO2 x solid solution can be combined with other representations of actinide and fission product containing fluorite UO2 phases to develop multi-component models within the CEF framework.
CALPHAD↗
New benzo[f]quinolino[3,4-b][1,7]naphthyridine-6,8(5H,9H)-diones: synthesis, electronic, molecular, and crystal structures. Protonation and complexation with lanthanum and europium salts
A series of novel benzo[f]quinolino[3,4-b][1,7]naphthyridine-6,8(5H,9H)-diones, which are promising ligands for the extractive separation of actinides and lanthanides, and also their complexes with lanthanum and europium were synthesized. The molecular and crystal structures of one among the ligands were determined by single crystal X-ray diffraction. The protonation of compounds was investigated by IR and NMR spectroscopy. The electronic structure of starting substances and protonated forms was estimated by DFT calculations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural and crystal chemical properties of rare-earth titanate pyrochlores
Rare-earth titanates, RE2Ti2O7 (where RE = a rare-earth) with the pyrochlore structure continue to be investigated for use as potential stable host materials for nuclear and actinide-rich wastes. Accordingly, the present work is directed towards the elucidation of the fundamental structural, physical, and thermochemical properties of this class of compounds. Single-crystals of the rare earth pyrochlores were synthesized using a high-temperature flux technique and were subsequently characterized using single-crystal X-ray diffraction. The cubic lattice parameters display an approximately linear correlation with the RE-site cation radius. Theoretical calculations of the lattice constants and bond lengths of the subject materials were carried out using density functional theory, and the results are compared to the experimental values. The Sm and Eu titanates exhibit a covalency increase between the REO8 and TiO6 polyhedra resulting in a deviation from the increasing linear lattice parameter through the transition series. Gd2Ti2O7 with the 4f7 half-filled f-orbital Gd3+ sub-shell exhibits the lowest 48f oxygen positional parameter. The coefficient of thermal expansion for the rare-earth titanate series is approximately linear, and it has a range of 10.1 11.2 x 10-6 C-1. Raman spectroscopy indicated that the ~530 cm-1 peak associated with the Ti-O stretching mode follows a general trend of decreasing frequency with increasing RE reduced mass.
crystal growth↗
An Overview of the Molten Salt Thermal Properties Database--Thermophysical, Version 3.1 (MSTDB-TP v.3.1)
This report presents the current status of the Molten Salt Thermal Properties Database–Thermophysical (MSTDB-TP). Information regarding version 3.1 is provided herein, which contains 820 individual salt entries (data from 180+ independent studies); the thermophysical properties contained in the database include density, viscosity, thermal conductivity, and heat capacity. The major updates to the database include a significant expansion of pseudobinary and higher-order chloride salt mixtures, many of which bearing actinides, and an incorporation of more recent literature data (i.e., that within the past 5 years). Also, modifications have been made to the pure compound data in the database as a consequence of an external quality assessment of duplicate datasets. The user-facing API for the MSTDB-TP, Saline, has been updated to include viscosity estimation capabilities based on the Redlich–Kister formalism; this is an advancement with respect to the existing density estimation capabilities. The graphical user interface was also updated to include a density estimation capability, backed by Saline. Finally, additional preliminary efforts to include surface tension into the database, as well as an investigation on formalisms that would be appropriate for thermal conductivity estimation, are reported herein.
36 MATERIALS SCIENCE↗