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All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Phase stability of some actinides with brannerite structure at high pressures

Structure behavior of actinide brannerites ThTi{sub 2}O{sub 6}, Y{sub 0.5}U{sub 0.5}Ti{sub 1.5}Nb{sub 0.5}O{sub 6} and their analog oxide CeTi{sub 2}O{sub 6} was studied at high pressure by using in situ x-ray diffraction, Raman scattering and infra-red absorption techniques, respectively. Brannerite structure was found to be not stable and started to become amorphous at pressures above 20 GPa. Some minor crystalline phase(s) due to phase decomposition was observed in all the three samples during pressurization. In addition, the observed bulk modulus indicated that the actinide-bearing brannerites are more compressible than their analog compound CeTi{sub 2}O{sub 6}, which may be related to the asymmetric 5f electron orbits of actinide elements. - Graphical abstract: Actinide-bearing compounds with brannerite structure and their analog CeTi{sub 2}O{sub 6} are not stable at high pressure. They were amorphized after {approx}20 GPa and a minor pressure-induced phase transition or decomposition process was always observed before amorphization. Highlights: > Phase stability of three brannerites CeTi{sub 2}O{sub 6}, ThTi{sub 2}O{sub 6}, and (U,Y)(Ti,Nb){sub 2}O{sub 6} at high pressures. > Brannerite structure was not stable and became amorphous after {approx}20 GPa. > Actinide-bearing brannerites are easier compressed than their analog compound CeTi{sub 2}O{sub 6}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Final Technical Report

During the past decades, considerable theoretical efforts have been devoted to studying the electronic and geometric structures and related properties of surfaces. Such efforts are particularly important for systems like the actinides for which experimental work is relatively difficult to perform due to material problems and toxicity. The actinides are characterized by a gradual filling of the 5f-electron shell with the degree of localization increasing with the atomic number Z along the last series of the periodic table. The open shell of the 5f electrons determines the atomic, molecular, and solid state properties of the actinide elements and their compounds and understanding the quantum mechanics of the 5f electrons is the defining issue in the chemistry and physics of actinide elements. These elements are also characterized by the increasing prominence of relativistic effects and their studies can, in fact, help us understand the role of relativity throughout the periodic table. However, the electronic and geometric structures of the actinides, specifically the trans-uranium actinides and the roles of the 5f electrons in chemical bonding are still not well understood. This is crucial not only for our understanding of the actinides but also for the fact that the actinides constitute 'the missing link' between the d transition elements and the lanthanides. The 5f orbitals have properties intermediate between those of localized 4f and delocalized 3d orbitals. Thus, a proper understanding of the actinides will help us understand the behavior of the lanthanides and transition metals as well. In fact, there is an urgent need for continued extensive and detailed theoretical research in this area to provide significant and deep understandings of the electronic and geometric structures of the actinides. In this work, we have performed electronic structure studies for plutonium (Pu), americium (Am), and curium (Cm) surfaces, and molecular adsorptions on Pu and Am surfaces. In particular, the region at the boundary of Pu and Am, is widely believed to be the crossover region between d-like itinerant and f-like localized behavior The eventual goal is a complete understanding of the surface chemistry and physics processes of all actinide surfaces, defining the chemistry and physics of such heavy elements. Among the actinides, plutonium, with five 5f electrons in the solid state, is arguably the most complex, fascinating, and enigmatic element known to mankind and has attracted extraordinary scientific and technological interests because of its unique properties, generating a significant body of research in diverse areas, including superconductivity. Pu has, at least, six stable allotropes between room temperature and melting at atmospheric pressure, indicating that the valence electrons can hybridize into a number of complex bonding arrangements. Central and critical questions relate to the electronic structure, localization of the 5f electrons and the magnetism of Pu. For the light-actinides, from Th to Pu, the 5f electrons are believed to be delocalized, hybridizing with the 6d and 7s electrons. For the heavier actinides, Am and beyond, the 5f electrons are localized with the 5f orbitals progressively lower in energy relative to the 6d configuration. Hence, Pu is in a position where the 5f electronic behavior changes from itinerant to localized. As far as magnetism is concerned, a majority of the theoretical calculations continues to claim the existence of magnetism while almost all the experimental results do not find any support for such claims. The second element of interest to us, namely americium, occupies a central position in the actinide series with respect to the involvement of 5f electrons in metallic bonding. It is widely believed that the 5f electrons in Am are localized and that Am undergoes a series of crystallographic phase changes with pressure. Fully-relativistic all electron surface studies of the different phases of Am, initially for the dhcp and the fcc surfaces, can and have provided us with valuable information about chemical bonding in Am and the transitions from f-electron delocalization to f-electron localization in trans-uranium compounds. In particular, a comparative study of the electronic structures of the Pu and Am surfaces using the techniques of all-electron modern density functional theory and beyond can provide significant information about the role of 5f electrons in bond formation as also the localization of the 5f electrons, matters of considerable controversies. The change from metallic 5f bonding into local-moment nonbonding configurations that takes place between Pu and Am is rather unique in the periodic table and is at the very heart of our understanding of electronic structure. We believe that, considering the narrow bandwidth of surface states, any transition from itinerant to localized behavior first takes place at the actinide surfaces with possible reconstructions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

A Macrocyclic Chelator That Selectively Binds Ln 4+ over Ln 3+ by a Factor of 10 29

A tetravalent cerium macrocyclic complex (CeLK 4 ) was prepared with an octadentate terephthalamide ligand comprised of hard catecholate donors and characterized in the solution state by spectrophotometric titrations and electrochemistry and in the crystal by X-ray diffraction. The solution-state studies showed that L exhibits a remarkably high affinity toward Ce 4+ , with log β 110 = 61(2) and ΔG = -348 kJ/mol, compared with log β 110 = 32.02(2) for the analogous Pr 3+ complex. In addition, L exhibits an unusual preference for forming CeL 4- relative to formation of the analogous actinide complex, ThL 4- , which has β 110 = 53.7(5). The extreme stabilization of tetravalent cerium relative to its trivalent state is also evidenced by the shift of 1.91 V in the redox potential of the Ce 3+ /Ce 4+ couple of the complex (measured at -0.454 V vs SHE). The unprecedented behavior prompted an electronic structure analysis using L 3 - and M 5,4 -edge X-ray absorption near-edge structure (XANES) spectroscopies and configuration interaction calculations, which showed that 4f-orbital bonding in CeLK 4 has partial covalent character due to ligand-to-metal charge transfer (LMCT) in the ground state. The experimental results are presented in the context of earlier measurements on tetravalent cerium compounds, indicating that the amount of LMCT for CeLK 4 is similar to that observed for [Et 4 N] 2 [CeCl 6 ] and CeO 2 and significantly less than that for the organometallic sandwich compound cerocene, (C 8 H 8 ) 2 Ce. A simple model to rationalize changes in 4f orbital bonding for tri- and tetravalent lanthanide and actinide compounds is also provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Electronic correlation and transport properties of nuclear fuel materials

The electronic structures and transport properties of a series of actinide monocarbides, mononitrides, and dioxides are studied systematically using a combination of density-functional theory and dynamical mean-field theory. The studied materials present different electronic correlation strength and degree of localization of 5f electrons, where a metal-insulator boundary naturally lies within. In the spectral function of Mott-insulating uranium oxide, a resonance peak is observed in both theory and experiment and may be understood as a generalized Zhang-Rice state. We also investigate the interplay between electron-electron and electron-phonon interactions, both of which are responsible for the transport in the metallic compounds. Our findings allow us to gain insight in the roles played by different scattering mechanisms, and suggest how to improve their thermal conductivities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

Novel Fundamental Building Blocks and Site Dependent Isomorphism in the First Actinide Borophosphates

Three novel uranyl borophosphates, Ag 2 (NH 4 ) 3 [(UO 2 ) 2 {B 3 O(PO 4 ) 4 (PO 4 H) 2 }]H 2 O (AgNBPU-1), Ag( 2-x )(NH 4 ) 3 [(UO 2 ) 2 {B 2 P 5 O (20-x) (OH) x }] (x = 1.26) (AgNBPU-2), and Ag (2-x) (NH 4 ) 3 [(UO 2 ) 2 {B 2 P (5-y) As y O (20-x) (OH) x }] (x = 1.43, y = 2.24) (AgNBPU-3), have been prepared by the H 3 BO 3 –NH 4 H 2 PO 4 /NH 4 H 2 AsO 4 flux method. The structure of AgNBPU-1 has an unprecedented fundamental building block (FBB), composed of three BO 4 and six PO 4 tetrahedra which can be written as 9□:[Φ] □⟨3□⟩□|□⟨3□⟩□|□⟨3□⟩□|. Two Ag atoms are linearly coordinated; the coordination of a third one is T-shaped. AgNBPU-2 and AgNBPU-3 are isostructural and possess a FBB of two BO 4 and five TO 4 (T = P, As) tetrahedra (7□:□⟨4□⟩□|□). AgNBPU-3 is a solid solution with some PO 4 tetrahedra of the AgNBPU-2 end-member being substituted by AsO 4 . Only two out of the three independent P positions are partially occupied by As, resulting in site dependent isomorphism. Finally, the three compounds represent the first actinide borophosphates.

actinides↗
DOE OSTI2023

Ring-Opening in the Actinide Cyclopropyl Complexes [Cp 3 U(2,2-Diphenylcyclopropyl)] n – ( n = 0, 1)

The reaction of [Cp 3 UCl] with in situ generated 1-lithium-2,2-dipenylcyclopropane results in the formation of [Cp 3 U(2,2-diphenylcyclopropyl)] (1) in good yield. Reduction of 1 with KC 8 , in the presence of 2.2.2-cryptand, results in the formation of a rare U(III) alkyl complex, [K(2.2.2-cryptand)][Cp 3 U(2,2-diphenylcyclopropyl)] (2). Thermolysis or photolysis of 1 for 10 d in toluene results in isomerization to the U(IV) η 1 -allyl complex, [Cp 3 U(η 1 -3,3-diphenylallyl)] (3). Moreover, photolysis of 2 in THF for 9 h at room temperature results in isomerization to the U(III) η 1 -allyl complex, [K(2,2,2-cryptand)][Cp 3 U(η 1 -3,3-diphenylallyl)] (4). Both 3 and 4 were fully characterized. Additionally, selective labeling of the C α positions of 1 and 2 with deuterium revealed that cyclopropyl ring-opening occurs via distal C–C bond cleavage via a hypothesized η 3 -allyl intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Pressure and temperature induced elastic properties of Am and Cf monobismuthides

The pressure and temperature dependent mechanical properties as melting temperature, hardness and brittle nature of XBi (X = Am and Cf) are studied. The rare earth actinides pnictides showed a structural phase transition (B1–B2) at a transition pressure (P{sub T}) of 14.3 GPa (AmBi) and 10.8 GPa (CfBi). Pressure dependence of melting temperature (T{sub m}) discerns an increase inferring the hardening or stiffening of the lattice as a consequence of bond compression and bond strengthening. Suppressed T{sub M} as functions of temperature infers the weakening of the lattice results in bond weakening in XBi (X = Am, Cf). Vickers Hardness (H{sub V}), Poisson’s and Pugh ratio of XBi (X = Am and Cf) demonstrates that XBi (X = Am and Cf) is mechanically stiffened, thermally softened and brittle on applied pressure and temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Crystal growth methods dedicated to low solubility actinide oxalates

Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 3}·xH{sub 2}O, Th(C{sub 2}O{sub 4}){sub 2}·6H{sub 2}O, M{sub 2+x}[Pu{sup IV}{sub 2−x}Pu{sup III}{sub x}(C{sub 2}O{sub 4}){sub 5}]·nH{sub 2}O and M{sub 1−x}[Pu{sup III}{sub 1−x}Pu{sup IV}{sub x}(C{sub 2}O{sub 4}){sub 2}·H{sub 2}O]·nH{sub 2}O. It is the first time that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV–visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds. - Graphical abstract: Two new single crystal growth methods dedicated to actinide oxalate compounds. - Highlights: • Use of diester as oxalate precursor for crystal growth of actinide oxalates. • Use of actinide oxide as precursor for crystal growth of actinide oxalates. • Crystal growth of Pu(III) and Am(III) oxalates. • Crystal growth of mixed Pu(III)/Pu(IV) oxalates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

ThH 5 : An Actinide–Containing Superhalogen Molecule

Thorium and its compounds have been widely investigated as important nuclear materials. Previous research focused on the potential use of thorium hydrides, such as ThH 2 , ThH 4 , and Th 4 H 15 , as nuclear fuels. Here, we report studies of the anion, ThH 5 , by anion photoelectron spectroscopy and computations. The resulting experimental and theoretical vertical detachment energies (VDE) for ThH 5 are 4.09 eV and 4.11 eV, respectively. These values and the agreement between theory and experiment facilitated the characterization of the structure of the ThH 5 anion and showed its neutral counterpart, ThH 5 to be a superhalogen. ThH 5 , which exhibits a C 4v structure with five Th–H single bonds, possesses the largest known H/M ratio among the actinide elements, M. Here, the adaptive natural density partitioning (AdNDP) method was used to further analyze the chemical bonding of ThH 5 – and to confirm the existence of five Th–H single bonds in the ThH 5 – molecular anion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Synthesis and Characterization of Tris-chelate Complexes for Understanding f -Orbital Bonding in Later Actinides

An isostructural family of f-element compounds (Ce, Nd, Sm, Gd; Am, Bk, Cf) of the redox-active dioxophenoxazine ligand (DOPOq; DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate) was prepared. This family, of the form M(DOPOq)3, represents the first nonaqueous isostructural series, including the later actinides berkelium and californium. The lanthanide derivatives were fully characterized using 1H NMR spectroscopy and SQUID magnetometry, while all species were structurally characterized by X-ray crystallography and electronic absorption spectroscopy. In order to probe the electronic structure of this new family, CASSCF calculations were performed and revealed these systems to be largely ionic in contrast to previous studies, where berkelium and californium typically have a small degree of covalent character. To validate the zeroth order regular approximation (ZORA) method, the same CASSCF analysis using experimental structures versus UDFT-ZORA optimized structures does not exhibit sizable changes in bonding patterns. This shows that UDFT-ZORA combined with CASSCF could be a useful first approximation to predict and investigate the structure and electronic properties of actinides and lanthanides that are difficult to synthesize or characterize.

Chemistry↗
DOE OSTI2019

Synthesis of Anhydrous Acetates for the Components of Nuclear Fuel Recycling in Dialkylimidazolium Acetate Ionic Liquids [plus supplemental information]

A series of anhydrous acetate salts with uranium {[C 2 C 1 im][UO 2 (OAc) 3 ] (1), [C 2 C 2 im][UO 2 (OAc) 3 ] (2), and [C 4 C 1 im][UO 2 (OAc) 3 ] (3)}, lanthanides {[C 2 C 2 im] 2 [La(OAc) 5 ] (4) and [C 2 C 1 im] 2 [Nd(OAc) 5 ] (5)}, and strontium {[C 2 C 1 im] n [Sr- (OAc) 3 ] n (6)} (where C 2 C 1 im = 1-ethyl-3-methylimidazolium, C 2 C 2 im = 1,3-diethylimidazolium, C 4 C 1 im = 1-butyl-3-methylimi-dazolium, and OAc = acetate) have been prepared and structurally characterized. Both lanthanides and strontium are common components of the nuclear fuel waste, and their separation from uranium is an important but still challenging task. A new synthetic method with dialkylimidazolium acetate ionic liquids (ILs) as the solvent has been developed for the direct synthesis of homoleptic acetates from the corresponding hydrates and, unexpectedly, hardly soluble f-element oxides. Although the group of characterized compounds shows perfect structural variability, all actinide and lanthanide metal ions form monomeric complex anions where the metal cation coordinates to five ligands including two oxygen atoms in the case of uranium, as is commonly observed for uranyl compounds. Crystallographic analyses revealed that the complex [UO 2 (OAc) 3 ] - anions possess rather standard D 3h symmetry featuring a hexagonal-bipyramidal coordination environment, while the lanthanide anions [Ln(OAc) 5 ] 2- are fully asymmetric and the Ln 3+ cations are 10-coordinated in the form of a distorted bicapped tetragonal antiprism. This is the first report of lanthanide ions coordinated in this fashion. For Sr 2+ , 9-fold coordination through oxygen atoms in the form of a strongly distorted tricapped trigonal prism is observed. Furthermore, the crystallization of anhydrous, homoleptic, anionic acetate complexes from such a large variety of different metal salts appears to be due to the properties of dialkylimidazolium acetate ILs themselves, including enhanced basicity from the high concentration of free anions and their greater affinity for hydrogen-bonding solutes relative to metal cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effects of Borate and Organics on U(VI) Solubility in WIPP Brine

The solubility of uranium (VI) in Waste Isolation Pilot Plant (WIPP)-relevant brine was determined to support ongoing WIPP recertification activities. This research was performed by the Los Alamos National Laboratory Carlsbad Operations (LANL-CO) Actinide Chemistry and Repository Science Program (ACRSP). The WIPP Actinide Source Term Program (ASTP) did not develop a model for the solubility of actinides in the VI oxidation state. The solubility of UO 2 2+ , in the absence of WIPP specific data, is presently set to be equal to a conservatively high 1 mM within the WIPP Performance Assessment (PA) for all expected WIPP conditions (SOTERM, 2019) as selected at the recommendation of the Environment Protection Agency (EPA) (EPA, 2005). According to the current WIPP chemistry model assumptions and conditions, the expected pC H+ is about 9.5 and controlled by MgO buffering CO 3 2- . The goal of this study is to perform screening experiments that account for the contributions of organics and borate on uranium solubility. In this report, the solubility of U(VI) was determined at pC H+ 9 WIPP brine in the absence or presence of borate and organics at under-saturation approach. Experiments were equilibrated for about 135 days. Organic compounds present in WIPP waste can form strong complexes with actinides and can affect the oxidation states of actinides. The organic compounds addressed in WIPP performance assessment include EDTA (Ethylenediaminetetraacetic Acid), oxalate, citrate, and acetate (SOTERM, 2019). These data quantify the effects of WIPP-relevant concentrations of borate and organics effects on the solubility of U(VI) to challenge the predictions of the WIPP actinide model and inform decisions and recommendations made in the upcoming recertification of the WIPP (CRA-2024). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Experimental Strategy to Challenge Actinide Solubility Predictions” and designated LCO-ACP-26. All data reported were obtained under the LANL-CO Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD) (QAPD, 2017).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

On reaction mechanisms involved in the deuteron–induced surrogate reactions

An extended analysis of the nuclear reaction mechanisms involved within deuteron interaction with nuclei, namely the breakup, stripping, pick-up, pre-equilibrium emission, and evaporation from fully equilibrated compound nucleus, is presented in order to highlight the importance of the direct mechanisms still neglected in the analysis of deuteron-induced surrogate reactions. Particularly, the dominance of the breakup mechanism at low energies around the Coulomb barrier should be considered in the case of (d,x) surrogate reactions on actinide target nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2012

Syntheses and crystal structures of the quaternary uranium lanthanide oxyselenides UYb{sub 2}O{sub 2}Se{sub 3} and U{sub 2}Ln{sub 2}O{sub 4}Se{sub 3} (Ln=Pr, Sm, Gd)

Single crystals of the new uranium lanthanide oxyselenide compounds UYb{sub 2}O{sub 2}Se{sub 3} and U{sub 2}Ln{sub 2}O{sub 4}Se{sub 3} (Ln=Pr, Sm, Gd) have been synthesized from an Sb{sub 2}Se{sub 3} flux. The structures have been determined from single-crystal X-ray diffraction data. UYb{sub 2}O{sub 2}Se{sub 3} is isostructural to UYb{sub 2}O{sub 2}S{sub 3}. The structure comprises layers of edge-sharing YbSe{sub 6} octahedra and double layers of disordered (U/Ln)O{sub 4}Se{sub 4} square antiprisms. The U{sub 2}Ln{sub 2}O{sub 4}Se{sub 3} (Ln=Pr, Sm, Gd) compounds are isostructural to U{sub 2}Ln{sub 2}O{sub 4}S{sub 3} (Ln=La-Gd) whose structure had been deduced previously from X-ray powder diffraction data. In the structure a dodecahedron of four O atoms and four Se atoms surrounds a site primarily occupied by U and a distorted bicapped octahedron of five Se atoms and three O atoms surrounds a site primarily occupied by the lanthanide. These compounds represent the first examples of quaternary uranium oxyselenides. - Graphical abstract: The U{sub 2}Ln{sub 2}O{sub 4}Se{sub 3} (Ln=Pr, Sm, Gd) structure: primarily U sites are in black, primarily Ln sites are in blue, O red, Se orange. Highlights: Black-Right-Pointing-Pointer Single crystals of the new compounds UYb{sub 2}O{sub 2}Se{sub 3} and U{sub 2}Ln{sub 2}O{sub 4}Se{sub 3} (Ln=Pr, Sm, Gd) have been synthesized. Black-Right-Pointing-Pointer These compounds represent the first examples of quaternary uranium oxyselenides. Black-Right-Pointing-Pointer U is surrounded by a dodecahedron or square prism of four O atoms and four Se atoms

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Interplay between London Dispersion, Hubbard U , and Metastable States for Uranium Compounds

High-throughput computational studies of lanthanide and actinide chemistry with density-functional theory are complicated by the need for Hubbard U corrections, which ensure localization of the f-electrons, but can lead to metastable states. This work presents a systematic investigation of the effects of both Hubbard U value and metastable states on the predicted structural and thermodynamic properties of four uranium compounds central to the field of nuclear fuels: UC, UN, UO 2 , and UCl 3 . We also assess the impact of the exchange-hole dipole moment (XDM) dispersion correction on the computed properties. Overall, the choice of Hubbard U value and inclusion of a dispersion correction cause larger variations in the computed geometric properties than result from metastable states. Further, the weak dependence of structure optimization on metastable states should simplify future high-throughput calculations on actinides. Conversely, addition of the dispersion correction is found to offset the repulsion introduced by the Hubbard U term and provides greatly improved agreement with experiment for both cell volumes and heats of formation. The XDM dispersion correction is largely invariant to the chosen U value, making it a robust dispersion correction for actinide systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Hill Plot Focusing on Ce Compounds with High Magnetic Ordering Temperatures and Consequent Study of Ce{sub 2}AuP{sub 3}

The Hill plot is a well-known criterion of the f-electron element interatomic threshold distance separating the nonmagnetic state from the magnetic state in actinides and lanthanides. We have reinvestigated the Hill plot of Ce compounds using the commercial crystallographic database CRYSTMET, focusing on a relationship between the Ce-Ce distance and the magnetic ordering temperature because a Ce compound with no other magnetic elements rarely has a magnetic ordering temperature that is higher than 20 K. The Hill plot of approximately 730 compounds has revealed that a Ce compound, particularly a ferromagnet, showing a high magnetic ordering temperature would require a short Ce-Ce distance with a suppression of the valence instability of the Ce ion. From the study, we developed interest in Ce{sub 2}AuP{sub 3} with a Curie temperature of 31 K. The ferromagnetic nature of this material has been examined in terms of a doping effect, which suggests a possible increase in magnetic anisotropy energy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

The roles of 4f- and 5f-orbitals in bonding: A magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

The electronic structures of 4f 3 /5f 3 Cp" 3 M and Cp" 3 M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(III) and uranium(III) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. As a result, while interaction with the isocyanide π*-orbitals lowers the energies of the 5f xz 2 and 5f yz 2- orbitals, spin–orbit coupling greatly reduces the population of 5f xz 2 and 5f yz 2 in the ground state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗