Bonding nature of the actinide tetrafluorides AnF4 (An = Th−Cm)

The knowledge of chemical bonding for actinide fluoride compounds is essential to understand and predict the physical and chemical behaviour of actinide elements in fluoride molten salt. In this work, the bonding nature of actinide tetrafluorides AnF₄ (An = Th?Cm) is investigated by using scalar relativistic density functional theory. Bond order analyses show relatively stronger An–F bonds for An = U?Np and weaker ones for An = Th, Am, and Cm. Despite the dominant ionic character of An–F bonds, a considerable covalent interaction is indicated by the overlap integral value of F 2p and actinide 5f, 6d orbitals. Both natural population analyses and electron density analyses show that An–F covalency rises initially before reducing in the latter systems with the maximum at Np and Pu and the obviously strong ionic bonding character in An = Th, Am, and Cm. Compared to AnCp₄ (Cp = η⁵–C₅H₅) reported in the literature, our study on AnF₄ suggests a much more prominent actinide–ligand covalent interaction. And the roles of orbital overlap and near-degeneracy in driving covalency are discussed.     

化合物SmCo5的电子结构、自旋和轨道磁矩及其交换作用分析

用自旋极化的MS-Xα方法研究了稀土-过渡族化合物SmCo5₅的电子态密度、自 旋能级劈裂及原子磁矩.研究结果显示，由于化合物中Sm-Co间的轨道杂化效应，使Sm原子原来的5d00空轨道上占据了少量5d电子.由于Co(3d)-Sm(5d)电子间的直接交换作用，导致了Sm-Co间的磁性交换耦合，这是化合物中形成Sm-Co铁磁性长程序的一个重要原因.在SmCo5_{5化合物中存在6个能级呈现负交换耦合，导致了SmCo55化 关键词： 电子结构 自旋极化 原子磁矩 交换耦合}     

Electronic structure and chemical bonding in actinide oxides: Monoxides and dioxides of Np,Pu, Am,Cm and Bk

First-principles molecular cluster calculations of the electronic structure of actinide monoxides and dioxides have been carried out in the local density formalism. AcO₆^10? clusters representative of monoxides and AcO₈^12? clusters for dioxides (Ac = Np, Pu, Am, Cm and Bk) have been studied in spin-restricted and spinpolarized models, using the discrete variational method with numerical atomic basis functions. One-electron energy level diagrams, atomic configurations, charge and spin densities were obtained. It is found that significant covalent mixing of O 2ρ and Ac 5f atomic orbitais occurs for heavy actinide compounds, contrary to the assumption of free-ion models. X-ray photoelectron line shape calculations agree rather well with experimental data on the dioxides. Analogies between systematics of the energy levels of actinide and rare-earth compounds are discussed.     

Orbital-selective Mott-insulator transition in Ca 2 - x Sr x RuO 4

The electronic structures of the metallic and insulating phases of the alloy series Ca_2-xSr_xRuO₄ ( 0 ? x ? 2) are calculated using LDA, LDA+U and Dynamical Mean-Field Approximation methods. In the end members the groundstate respectively is an orbitally non-degenerate antiferromagnetic insulator (x = 0) and a good metal (x = 2). For x > 0.5 the observed Curie-Weiss paramagnetic metallic state which possesses a local moment with the unexpected spin S = 1/2, is explained by the coexistence of localized and itinerant Ru-4d-orbitals. For 0.2 < x < 0.5 we propose a state with partial orbital and spin ordering. An effective model for the localized orbital and spin degrees of freedom is discussed. The metal-insulator transition at x = 0.2 is attributed to a switch in the orbital occupation associated with a structural change of the crystal. Received 27 July 2001     

Study of the ferrodistorsive orbital ordering in NaNiO2 by neutron diffraction and submillimeter wave ESR

NaNiO₂ has been studied by neutron-powder diffraction, magnetic susceptibility and submillimeter wave ESR. The monoclinic structure at room temperature is characterised by a ferrodistorsive orbital ordering due to the Jahn-Teller (JT) effect of the Ni³⁺ ions in the low spin state. NaNiO₂ undergoes a structural transition at around 480 K, above which the orbital ordering disappears. The high temperature phase is rhombohedral with the layered -NaFeO₂ structure ( space group). The magnetic susceptibility exhibits hysteresis and we observe a change of the Curie-Weiss law parameters above the JT transition. The anisotropy of the g-factor at 200 K can be attributed to the JT effect which favours the orbital occupation. Finally, the interplay between the magnetic and structural properties of NaNiO₂ and Li_1-xNi_1+xO₂ is discussed. Received 29 May 2000     

Soft X-ray magnetic circular dichroism in Fe and Fe 0.50 Co 0.48 V 0.02 films: quantitative analysis of transmission

Magnetic circular dichroism (MCD) in X-ray absorption has been measured at the L _{2, 3} edges of Fe in ex-situ grown Fe and Fe _0.50 Co _0.48 V _0.02 films by means of the transmission method. A new approach is developed for fitting the observed transmittance, which describes the resonance lineshapes as (generalized) Fano profiles. Analytical integration of each single resonance allows a more reliable determination of the orbital and spin magnetic moments based on the MCD sum rules. The results are consistent with an increase of the Fe spin and orbital magnetic moment in Fe-Co alloys as obtained by other experiments and band structure calculations. Received 15 August 2000 and Received in final form 11 June 2001     

High-pressure phases of plutonium monoselenide studied by X-ray diffraction

Abstract

Plutonium monoselenide was studied under high pressure up to 47 GPa, at room temperature, using a diamond anvil cell in an energy dispersive X-ray diffraction facility. At ambient pressure, PuSe has the NaC1-type (B1) structure. The compound has been found to undergo a second-order crystallographic phase transition at around 20 GPa. This phase can be described as a distorted B1 structure, with a rhombohedral symmetry. PuSe transforms to a new phase at around 35 GPa, which can be indexed in the cubic CsCl-type (B2). The volume collapse at this phase transition is 11%. When releasing pressure, we observed a strong hysteresis to the inverse transformation down to 5 GPa. From the pressure-volume relationship, the bulk modulus has been determined to B ₀ = 98 GPa and its pressure derivative as B ₀ = 2.6. These results are compared to those obtained with other actinide monmictides and monochalcogenides.     

Coulomb‐enhanced spin–orbit coupling and semiconductor to half‐metal transition under pressure in Sr2CrReO6

Ordered Sr₂CrReO₆ has been synthesized recently. It is measured to be ferrimagnetic semiconductor, in contrary to the previous reports of metallic properties. To solve the discrepancy, we have investigated the compound by using the density functional theory. The semiconducting behavior is reproduced by including the electron correlation and spin–orbit coupling simultaneously. The calculated band gap is 0.22 eV, close to the experimental value of 0.21 eV. A large orbital moment of 0.69µ_B is found for Re, which is caused by the Coulomb‐enhanced spin–orbit coupling. By applying pressure, a semiconductor to half‐metal transition is observed through 5% volume compression.

     

Spin fluctuations in metals: Application to the actinides

We present here a review of the spin fluctuation theory and of its applications to transition and actinide systems, with a particular emphasis to the latter where some very anomalous properties find an explanation in terms of spin fluctuation effects. Firstly, we summarize the development of the spin fluctuation model which had been initially applied to transition metals and alloys such as palladium or Pd–Ni alloys. Then, we present the extension of the paramagnon model to nearly magnetic actinide systems by taking into account explicitly the temperature dependence of the Stoner susceptibility, because the 5f-band of actinides is much narrower than the d-band of transition metals. As a result the paramagnon contribution to the resistivity departs from the usual T ² and T power laws at temperatures higher than the spin fluctuation one and saturates at high temperatures, with eventually the presence of a maximum at intermediate temperatures. We present also the calculation of the other properties of actinide systems, namely the thermal resistivity, the thermoelectric power, the magnetic susceptibility, the specific heat capacity and the NMR relaxation rate, which are generally enhanced by the presence of paramagnons. Finally, we have introduced the concept of ‘antiferromagnetic-like’ spin fluctuations which have a maximum of the q-dependent susceptibility _χ(q) at a q value different from q =0, in contrast to the regular ferromagnetic spin fluctuations; both types of spin fluctuation give the same resistivity behaviour, while they yield a markedly different behaviour of the magnetic susceptibility, in agreement with experiment. The spin fluctuation theory is applied successfully to the different properties of neptunium and plutonium metals and of many nearly magnetic compounds such as UAl₂.     

Spin re-orientation in FeCr2S4

The spinel FeCr₂S₄has been studied intensely for its peculiar magnetic and local structural changes which are sensitively influenced by the Jahn?CTeller properties of Fe^2?+?in tetrahedral sulfur coordination. Recent muon spin rotation data give strong evidence that the commonly assumed collinear magnetic structure of this compound is only found between the Curie temperature T_C = 165 K and 50 K. For lower temperatures a helical structure has been proposed. We present new Mössbauer spectroscopic data taken on the same sample as used for muon spin rotation. Also the hyperfine spectra revealing non-equivalent iron sites support the appearance of a spin re-orientation around 50 K which may be related to the onset of short-range orbital order. Below 20 K severe dynamic broadenings are found which may indicate orbital fluctuations. Orbital order occurs around 11 K accompanied by severe changes in the crystalline electric field ground state as traced from quadrupole interaction.     

Random anisotropy in R2CuO4 (R=Nd, Pr, Sm, Gd, Eu) quasi-2D antiferromagnets

The mechanisms of random anisotropy produced by an an effective coupling between rare-earth ion moments and orbital momenta of Cu₂₊ ions through spin fluctuations is studied in R₂CuO₄ crystals. The effective random-anisotropy fields are estimated from an analysis of experimental data for R₂CuO₄ crystals (R=Eu, Pr, Gd). Fiz. Tverd. Tela (St. Petersburg) 41, 1259–1263 (July 1999)     

High Pressure Theoretical Studies of Actinide Dioxides

Actinide dioxides (ThO 2 , UO 2 , Pu 2 etc.) compounds have the CaF 2 -type structure at ambient pressure and temperature. Under high pressure, they exist in the PbCl 2 -type structure, belonging to space group Pnma [1]. We have studied crystal structures under high pressure in actinide dioxides by means of first-principles self-consistent total-energy calculations with the non-local Perdew, Burke and Ernzerhof (PBE) exchange correlation using the full-potential linear-muffin-tin-orbital (FPLMTO) method. The atomic equilibrium volume, bulk modulus and transition pressure for actinide dioxides were calculated, covering the full pressure range for which the mentioned experiments have been done [2].     

Structural phase transition in the 2D spin dimer compound SrCu 2 ( BO 3 ) 2

A displacive, 2nd order structural phase transition at T _s = 395 K from space group I 2 m below T _s to I 4/m c m above T _s has been discovered in the two-dimensional spin dimer compound SrCu₂(BO₃)₂. The temperature evolution of the structure in both phases has been studied by X-ray diffraction and Raman scattering, supplemented by differential scanning calorimetry and SQUID magnetometry. The implications of this transition and of the observed phonon anomalies in Raman scattering for spin-phonon and interlayer coupling in this quantum spin system will be discussed. Received 24 July 2000 and Received in final form 2 November 2000     

Covalent magnetism in the RFe <Emphasis Type="Bold">6</Emphasis>Ge <Emphasis Type="Bold">6</Emphasis> series

The electronic structure of the RFe ₆ Ge ₆ compounds ( R = Sc, Lu, Ti, Zr, Hf and Nb) of HfFe ₆ Ge ₆ -type structure has been studied using the muffin-tin Korringa-Kohn-Rostoker method in a non-relativistic approach. The chemical bonding is analyzed based on the l-decomposed site projected densities of states. Spin-dependent changes in the R nd- Fe 3d covalent bond are shown to be responsible for the experimentally observed rise in the Fe moment and hyperfine field upon increasing the R valency. The limited quantitative agreement between theoretical and experimental values is interpreted as being due to a non-negligible orbital moment and to a significant asphericity in the spin density at the iron site. The theoretical results also forecast a strong increase of the Ge(2e) transferred hyperfine field with the R valency. Received 20 December 2002 Published online 4 June 2003 RID="a" ID="a"e-mail: Thomas.Mazet@lcsm.uhp-nancy.fr RID="b" ID="b"Associé au CNRS (UMR 7555)     

The 59Co nuclear magnetic resonances in the intermetallic compounds

The anisotropic hyperfine fields of the intermetallic compounds have been studied by the spin echo method and were obtained from the NMR spectra of ⁵⁹Co nuclei in ThCo₅ and YCo₅ which have the high anisotropy fields resulting from the orbital moments. The intermetallic compounds, ThCo_5.3 and YCo_5.3, have been also investigated.     

Electron-energy-loss spectroscopy and X-ray absorption spectroscopy as complementary probes for complex f-electron metals: cerium and plutonium

In this paper, we demonstrate the power of electron-energy-loss spectroscopy (EELS) in a transmission electron microscope by investigating the electron structure of two f-electron metals: Ce and Pu. It is shown that EELS in a transmission electron microscope may be used to circumvent the difficulty of producing single-phase or single-crystal samples owing to its high spatial resolution, and that diffraction patterns and images can be acquired, providing unambiguous phase determination when acquiring spectra. EELS results are supported by synchrotron-radiation-based X-ray absorption, multielectron atomic spectral simulations, and local density approximation calculations based on density-functional theory with the generalized gradient approximation. For Ce, it is shown that changes in {111} stacking sequences can drive substantial modifications in the electronic structure of close-packed phases of Ce that have similar atomic volumes, contrary to previous assumptions in literature. For Pu, it is shown that Russell–Saunders (L–S) coupling fails for the 5f states and that either a j–j or an intermediate scheme must be used for the actinides because of the considerable spin–orbit interaction in the 5f states. We present a model showing how the 5f states behave along the light actinide series.     

Structural,elastic, thermodynamic and electronic properties of LuX (X = N,Bi and Sb) compounds: first principles calculations

ABSTRACT

The structural, electronic, elastic and thermodynamic properties of LuX (X = N, Bi and Sb) based on rare earth into phases, Rocksalt (B1) and CsCl (B2) have been investigated using full-potential linearized muffin-tin orbital method (FP-LMTO) within density functional theory. Local density approximation (LDA) for exchange-correlation potential and local spin density approximation (LSDA) are employed. The structural parameters as lattice parameters a₀, bulk modulus B, its pressure derivate B’ and cut-off energy (E_c) within LDA and LSDA are presented. The elastic constants were derived from the stress–strain relation at 0 K. The thermodynamic properties for LuX using the quasi-harmonic Debye model are studied. The temperature and pressure variation of volume, bulk modulus, thermal expansion coefficient, heat capacities, Debye temperature and Gibbs free energy at different pressures (0–50 GPa) and temperatures (0–1600 K) are predicted. The calculated results are in accordance with other data.     

Solution of the problem of catastrophic relaxation of homogeneous spin precession in superfluid 3He-B

The quantitative analysis of the “catastrophic relaxation” of the coherent spin precession in ³He-B is presented. This phenomenon has been observed below a temperature of about 0.5 T _c as an abrupt shortening of the induction signal decay. It is explained in terms of the decay instability of the homogeneous transverse NMR mode into spin waves of the longitudinal NMR. Recently, the cross interaction amplitude between the two modes has been calculated by Sourovtsev and Fomin [9] for the so-called Brinkman-Smith configuration, i.e., for the orientation of the orbital momentum of Cooper pairs along the magnetic field, L ‖ H. In their treatment, the interaction is caused by the anisotropy of the speed of the spin waves. We found that, in the more general case of the nonparallel orientation of L corresponding to the typical conditions of the experiment, the spin-orbital interaction provides the additional interaction between the modes. By analyzing the experimental data, we are able to distinguish which contribution is dominating in different regimes. The text was submitted by the authors in English.