Actinide Chalcogenides Research Articles

Synthesis of uranium mixed anion compounds synthesized using the Boron-Chalcogen Mixture method: Ba6Co6U0·91S13·5O0.5 and Ba5·47K0·53Zn6US13·5O0.5

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 Ba2MUO6 (M = Co, Zn) which resulted in two new uranium (IV/V) oxysulfide compounds, Ba6Co6U0·91S13·5O0.5 and Ba5·47K0·53Zn6US13·5O0.5 These compounds crystallize in the tetragonal crystal system adopting the space group I4/mcm. Their syntheses, crystal structures, and trends observed in the pursuit of these new mixed anion compounds are reported.

Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCuTS3 Family.

The behavior of 5f electrons in soft ligand environments makes actinides, and especially transuranium chalcogenides, an intriguing class of materials for fundamental studies. Due to the affinity of actinides for oxygen, however, it is a challenge to synthesize actinide chalcogenides using non-metallic reagents. Using the boron chalcogen mixture method, we achieved the synthesis of the transuranium sulfide NaCuNpS3 starting from the oxide reagent, NpO2. Via the same synthetic route, the isostructural composition of NaCuUS3 was synthesized and the material contrasted with NaCuNpS3. Single crystals of the U-analogue, NaCuUS3, were found to undergo an unexpected reversible hydration process to form NaCuUS3·xH2O (x ≈ 1.5). A large combination of techniques was used to fully characterize the structure, hydration process, and electronic structures, specifically a combination of single crystal, powder, high temperature powder X-ray diffraction, extended X-ray absorption fine structure, infrared, and inductively coupled plasma spectroscopies, thermogravimetric analysis, and density functional theory calculations. The outcome of these analyses enabled us to determine the composition of NaCuUS3·xH2O and obtain a structural model that demonstrated the retention of the local structure within the [CuUS3]- layers throughout the hydration-dehydration process. Band structure, density of states, and Bader charge calculations for NaCuUS3, NaCuUS3·xH2O, and NaCuNpS3 along with X-ray absorption near edge structure, UV-vis-NIR, and work function measurements on ACuUS3 (A = Na, K, and Rb) and NaCuUS3·xH2O samples were carried out to demonstrate that electronic properties arise from the [CuTS3]- layers and show surprisingly little dependence on the interlayer distance.

Covalency in Actinide Compounds.

Covalency in actinides has emerged as a resounding research topic on account of the technological importance in separating minor actinides from lanthanides for spent nuclear fuel processing, and utilization of their distinct bonding properties has been realized as a route towards overcoming this challenge. Because of the limited radial extent of the 4f orbitals, there is almost no 4f electron participation in bonding in lanthanides; this is not the case for the actinides, which have extended 5f orbitals that are capable of overlapping with ligand orbitals, although not to the degree of overlap as in the d orbitals of transition metals. In this concept paper, a general description of covalency in actinide compounds is provided. After introducing two main approaches to enhance covalency, either by exploiting increased orbital overlap or decreasing energy differences between the orbitals causing orbital energy degeneracy, the current state of the field is illustrated by using several examples from the recent literature. This paper is concluded by proposing the use of actinide chalcogenides as a convenient auxiliary tool to study covalency in actinide compounds.

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. 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 functionality 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 transformation in solid-state reactions, and in situ generation of actinide chalcogenides in flux crystal growth reactions.

Overview of the crystal chemistry of the actinide chalcogenides: incorporation of the alkaline-earth elements.

This review focuses on the results of exploratory syntheses of alkaline-earth-metal actinide chalcogenides Ak-An-Q (Ak = Ba, Sr; An = Th, U; Q = S, Se, and Te). About thirty new compounds are described. Although the basic building blocks of their structures are usually AnQ6 octahedra and AkQ8 bicapped trigonal prisms, these are combined in diverse ways to afford eleven new structure types. The structures reconfirm the prevailing presence of An4+ in chalcogenides, although some of the compounds discovered are mixed An4+/An5+ systems, and a few contain only An5+. The tendency of the chalcogens to form Q-Q bonds is again evident from the presence of S-S single bonds and infinite Te-Te-Te linear chains. The latter possess interatomic distances of lengths greater than that of a Te-Te single bond but less than that of a Te-Te van der Waals interaction. Assignment of formal oxidation states in compounds containing these chains is arbitrary at best. Addition of metal atoms (M) affords quaternary structures, some of which show remarkable flexibility in the positions of the An and M atoms, and in such compounds the nature of the M elements influences directly the dimensionality of the resultant structure. The presence of adventitious oxygen, often from etching of the fused-silica tubes by oxyphilic An elements, results in new quintary compounds that show remarkable structural variations with change of M. The compounds discussed have shown transport and electronic structures that range from metallic-like to semiconducting. We find, with the exception of BaUSe3, when comparisons can be made that the values of the calculated band gaps are reasonably close but usually lower than the experimentally derived values. Thus the method used, in particular the HSE functional, has been generally successful on these 5f actinides. This is an important result because in the absence of suitable crystals, and hence experimental measurements, it still may be possible to offer credible predictions of some of the magnetic and electronic properties of the compounds.

Four new actinide chalcogenides Ba2Cu4USe6, Ba2Cu2ThSe5, Ba2Cu2USe5, and Sr2Cu2US5: crystal structures and physical properties.

Four new actinide chalcogenides—namely, Ba2Cu4USe6, Ba2Cu2ThSe5, Ba2Cu2USe5, and Sr2Cu2US5—were synthesized via solid-state methods at 1173 K. Single-crystal X-ray diffraction studies show that Ba2Cu4USe6 crystallizes in a new structure type in space group C2h5–P21/c of the monoclinic system, whereas the three other compounds are isostructural and adopt the Ba2Cu2US5 structure type in space group C2h3–C2/m, also of the monoclinic system. These Ak/Cu/An/Q structures (Ak = alkaline-earth metal; An = actinide; Q = chalcogen) have no short Q–Q interactions and, hence, are charge-balanced with Ak2+, Cu1+, An4+, and Q2–. Crystal structures of all these compounds are two-dimensional and feature layers that are separated by Ba2+ cations. The compositions of these layers differ. In the structure of Ba2Cu4USe6, the ∞2[Cu4USe64–] layers comprising USe6 octahedra and CuSe4 tetrahedra stack perpendicular to the a-axis. These ∞2[Cu4USe64–] layers show short Cu–Cu interactions. In the three isostructural Ak2Cu2AnQ5 compounds, AnQ6 octahedra and CuQ4 tetrahedra are connected along the c-axis in the sequence “...oct tet tet oct tet tet...” to form the ∞2[Cu2AnQ54–] layers. Resistivity, optical, and DFT calculations show semiconducting behavior for these compounds.

Three new quaternary actinide chalcogenides Ba2TiUTe7, Ba2CrUTe7, and Ba2CrThTe7: syntheses, crystal structures, transport properties, and theoretical studies.

The three new quaternary actinide chalcogenides Ba2TiUTe7, Ba2CrUTe7, and Ba2CrThTe7 have been synthesized. From single-crystal X-ray diffraction studies these isostructural compounds are found to crystallize in a new structure type in space group D2h16–Pnma of the orthorhombic system. The structure features ∞1[MAnTe74–] strips (M = Cr or Ti; An = Th or U) that propagate in the b-direction and are separated by Ba cations. An atoms are coordinated to eight Te atoms in a bicapped trigonal-prismatic geometry while M atoms are octahedrally coordinated to six Te atoms. Sharing of the AnTe8 and MTe6 polyhedra forms ∞1[MAnTe74–] strips. The presence of the infinite linear Te–Te–Te chains in these compounds makes assignment of oxidation states arbitrary. Resistivity measurements and DFT calculations provide further insight into the properties of these compounds.

Ba2An(S2)2S2(An = U, Th): Syntheses, Structures, Optical, and Electronic Properties

The compounds Ba2An(S2)2S2 (An = U, Th) have been synthesized by reactions of the elements with BaS and S at 1273 and 1173 K, respectively. These isostructural compounds crystallize in a new structure type in the tetragonal space group D(4h)(15)-P42/nmc. The structure comprises Ba2+ cations and (∞)(2)[An(S2)2(S)2(4–)] layers. The An4+ cations in these layers are arranged linearly and are bridged by S2– anions. Coordination about the An center, which has symmetry 4m2, consists of two S2(2–) ions and four S2– ions. Thus, the compounds are charge-balanced with An4+. No other alkali-metal actinide chalcogenides are known that contain chalcogen–chalcogen bonds. Optical measurements on Ba2Th(S2)2S2 indicate a direct band gap of 2.46(5) eV. Density functional theory calculations, performed with the HSE exchange-correlation potential, lead to band gaps of 2.2 and 1.8 eV for Ba2Th(S2)2S2 and Ba2U(S2)2S2, respectively, thus demonstrating the utility of applying this functional to 5f-electron systems.

Pentavalent and Tetravalent Uranium Selenides, Tl3Cu4USe6and Tl2Ag2USe4: Syntheses, Characterization, and Structural Comparison to Other Layered Actinide Chalcogenide Compounds

The compounds Tl(3)Cu(4)USe(6) and Tl(2)Ag(2)USe(4) were synthesized by the reaction of the elements in excess TlCl at 1123 K. Both compounds crystallize in new structure types, in space groups P2(1)/c and C2/m, respectively, of the monoclinic system. Each compound contains layers of USe(6) octahedra and MSe(4) (M = Cu, Ag) tetrahedra, separated by Tl(+) cations. The packing of the octahedra and the tetrahedra within the layers is compared to the packing arrangements found in other layered actinide chalcogenides. Tl(3)Cu(4)USe(6) displays peaks in its magnetic susceptibility at 5 and 70 K. It exhibits modified Curie-Weiss paramagnetic behavior with an effective magnetic moment of 1.58(1) μ(B) in the temperature range 72-300 K, whereas Tl(2)Ag(2)USe(4) exhibits modified Curie-Weiss paramagnetic behavior with μ(eff) = 3.4(1) μ(B) in the temperature range 100-300 K. X-ray absorption near-edge structure (XANES) results from scanning transmission X-ray spectromicroscopy confirm that Tl(3)Cu(4)USe(6) has Se bonding characteristic of discrete Se(2-) units, Cu bonding generally representative of Cu(+), and U bonding consistent with a U(4+) or U(5+) species. On the basis of these measurements, as well as bonding arguments, the formal oxidation states for U may be assigned as +5 in Tl(3)Cu(4)USe(6) and +4 in Tl(2)Ag(2)USe(4).

Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

The gas-phase thermochemistry of actinide monosulfides, AnS, was investigated experimentally and theoretically. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the reactivity of An(+) and AnO(+) (An = Th, Pa, U, Np, Pu, Am and Cm) with CS(2) and COS, as well as the reactivity of the produced AnS(+) with oxidants (COS, CO(2), CH(2)O and NO). From these experiments, An(+)-S bond dissociation energies could be bracketed. Density functional theory studies of the energetics of neutral and monocationic AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm) provided values for bond dissociation energies and ionization energies; the computed energetics of neutral and monocationic AnO were also obtained for comparison. The theoretical data, together with comparisons with known An(+)-O bond dissociation energies and M(+)-S and M(+)-O dissociation energies for the early transition metals, allowed for the refining of the An(+)-S bond dissociation energy ranges obtained from experiment. Examination of the reactivity of AnS(+) with dienes, coupled to comparisons with reactivities of the AnO(+) analogues, systematic considerations and the theoretical results, allowed for the estimation of the ionization energies of the AnS; the bond dissociation energies of neutral AnS were consequently derived. Estimates for the case of AcS were also made, based on correlations of the data for the other An and the electronic energetics of neutral and ionic An. The nature of the bonding in the elementary molecular actinide chalcogenides (oxides and sulfides) is discussed, based on both the experimental data and the computed electronic structures. DFT calculations of ionization energies for the actinide atoms and the diatomic sulfides and oxides are relatively reliable, but the calculation of bond dissociation energies is not uniformly satisfactory, either with DFT or CCSD(T). A key conclusion from both the experimental and theoretical results is that the 5f electrons do not substantially participate in actinide-sulfur bonding. We emphasize that actinides form strikingly strong bonds with both oxygen and sulfur.

Correlation effects in electronic structure of actinide monochalcogenides

We have implemented a technique for realistic electronic structure calculations of $f$-electron systems with moderately strong correlations. The technique is based on the dynamical mean-field theory with a perturbative treatment of effective quantum impurity problem in a spin-polarized version of the $T$ matrix combined with the fluctuating exchange approximation (SPTF). The present many-body approach properly includes the effects of strong spin-orbit coupling. We have used this technique for the dynamic mean-field theory (DMFT) calculations of ferromagnetic (USe, UTe) and nonmagnetic (PuSe, PuTe) actinide chalcogenides. In the static limit, the local-density approximation $(\mathrm{LDA})+\mathrm{U}$ method correctly reproduces the ground-state magnetic properties of these compounds, but fails to describe their spectral properties. Dynamical correlation effects drastically improve the agreement between theoretical densities of states and experimental photoemission spectra for the systems under consideration.

Electronic and elastic properties of the light actinide tellurides

The elastic constants c 11, c 12 and c 44 of U, Np, Pu, and Am telluride single crystals have been obtained by Brillouin scattering from the measured sound velocities in prominent crystallographic directions. In case of the U chalcogenides also by ultrasound techniques. The Cauchy pressure, the Poisson ratio, the anisotropy ratio, the bulk modulus and the Debye temperature have been derived from these data. U and Pu telluride have a negative c 12, implying intermediate valence. AmTe has a very low bulk modulus, but a positive c 12. It is extremely soft, with a very low sound velocity. For AmTe also the LO and TO phonon frequencies could be determined. The elastic data point to a divalent Am state. The optical reflectivity of the light actinide tellurides (and sometimes of all chalcogenides) has been measured between UV and infrared wavelengths, in the case of AmTe down to the far infrared. The plasma edge of the free carriers has been determined, which yields the ratio of n/ m*. Together with the γ value of the specific heat and magnetic data a consistent proposal for the electronic structure of the light actinide chalcogenides can be given. Thus, the Pu chalcogenides are intermediate valent and represent the high-pressure phase of the corresponding Sm chalcogenides. AmTe, as judged by the electronic, optic and magnetic properties seems to be in the 5f 7 configuration, i.e. divalent Am, but with a narrow, half-filled (24 meV) wide 5f band, about 0.1 eV below the bottom of the 6d conduction band. We thus propose a new kind of unhybridized heavy fermion. Also AmTe seems to represent a high-pressure phase of EuTe.

Techniques of preparation and crystal chemistry of transuranic chalcogenides and pnictides

The crystal chemistry of a number of transuranic chalcogenides and pnictides has been investigated using /sup 243/Am, /sup 248/Cm, /sup 249/Bk, and /sup 249/Cf. These compounds were prepared from the corresponding metals by direct reaction with the chalcogen or pnictogen element at elevated temperatures. Higher chalcogenides were thermally dissociated to yield ones of lower stoichiometry, terminating with the sesquichalcogenides; only monopnictides of these transplutonium elements were found. All products were examined by x-ray powder diffraction. In this paper the methods for preparing the actinide chalcogenides and pnictides on a gram scale are reviewed, and the microtechniques used for submilligram quantities of the transamericium elements are presented. The results obtained during this study are compared to data previously reported for the lighter actinide compounds, and the trends observed across the series are discussed.

Actinide chalcogenides and pnictides. III. Optical-phonon frequency determination in UX and ThX compounds by neutron scattering

For pt. II see abstr. A44356 of 1973. The optical-phonon branch in actinide compounds is flat provided there is both a large mass difference between the actinide ion and the lighter anion and negligible interaction between neighbouring anions. For such a compound the neutron time-of-flight spectrum using a polycrystalline sample will give a sharp peak at the optical frequency. This concept is used here in measuring the mean optical frequency for nine AnX compounds with the rock-salt structure where An=U and Th and X=C, N, P, S and Se. The optical frequency is interpreted in terms of a single nearest-neighbour An-X force constant. It is found that the U-X force constants are 20-30% higher than the corresponding Th-X force constants. In both cases the constants increase with the An-X separation. UC and ThC have anomalously low force constants.