Electronic structure of Pu monochalcogenides and monopnictides

The electronic and magnetic properties of Pu monopnictides and monochalcogenides, PuX (X = N, P, As, Sb, Bi, O, S, Se, Te, Po), are studied using the self-interaction-corrected local spin-density approximation. This approach allows for an integer number of f-states to be localized, while the remaining f-electron degrees of freedom are available for band formation. By varying the relative proportions of localized and delocalized f-states, the energetically most favourable (groundstate) configuration can be established. We show that the experimental data can be interpreted in terms of the coexistence of both localized and delocalized f-states. Received 10 August 2001     

Study of high pressure behavior and elastic properties of praseodymium monochalcogenides and monopnictides

The structural and elastic properties of praseodymium monochalcogenides (PrX: X = S, Se, Te) and monopnictides (PrY: Y = P, As, Sb, Bi) with NaCl-type structure have been investigated by using an interionic potential theory with necessary modification to include the effect of Coulomb screening due to the delocalized f-electrons of rare earth ion. The calculations are done at ambient as well as at high pressure. The structure of the high pressure phase of PrX compounds is CsCl-type while all the PrY compounds have been found to undergo from their initial NaCl-type structure to high pressure body centered tetragonal (BCT) structure, which can be seen as the distorted CsCl-type with c/a ratio ≈ 0.82–0.87. The calculated transition pressures are in good agreement with the experimental results. The elastic properties like second-order elastic constants for PrX, Y compounds are calculated for the first time. The nature of the bonding is also predicted by calculating the distance between the ions with the increasing pressure.     

Ab initio investigation of uranium monochalcogenides

We present ab initio investigation of the electronic structure and magnetic properties of uranium monochal-cogenides: US, USe, UTe. The calculations were performed by using the recently developed LDA+U+SO method in which both Coulomb and spin-orbit interactions have been taken into account in rotationally invariant form. We discuss the problem of choice of the Coulomb interaction value. The calculated [111] easy axes agree with those experimentally observed. The electronic configuration 5f ³ was found for all uranium compounds under investigation.     

Bulk moduli and high-pressure phases of the uranium rocksalt structure compounds: II. The monopnictides

Abstract

The high-pressure crystal structures of the compounds UX, where X = N, P, As and Sb, have been studied using X-ray diffraction in the pressure range up to about 60 GPa Rhornbohedral distortions are observed for UN and Up above 29 GPa and lO GPa, respectively. In Up a further transformation to an orthorhombic phase occurs at 28 GPa. UAs and USb transform to the CsCl structure at 20 GPa and 9 GPa, respectively. The latter transformations show a considerable hysteresis when the pressure is released. The scaling behaviour of the bulk modulus has been studied. It is confirmed that a log-log plot of bulk modulus versus specific volume for the cubic phases gives a straight line with a slope near ? 5/3.     

ESR study of exchange parameters in praseodymium monochalcogenides and monopnictides: Correlation with a pressure experiment

The exchange interaction between gadolinium ions and the host praseodymium ions in praseodymium monochalcogenides does not vary considerably across the chalcogenide series as it does in the case of the Van Vleck pnictides. The existence of a correlation between these results and a previous pressure study by Guertin et al. is pointed out.     

High pressure structural phase transition in uranium monochalcogenides

The pressure induced phase transition in uranium monochalcogenides, UX (X = S, Se, and Te) is studied by two-body potential approach. It is found that US, USe and UTe undergo a structural phase transition from NaCl (B1) type to CsCl (B2) type at 78.5, 21 and 9.5 GPa, respectively, which is in good agreement with the recent experimental data. In addition, second-order elastic constants (SOECs) (C ₁₁, C ₁₂ and C ₁₄) have been calculated which can be used to establish the nature of the forces in these materials. The present study shows that the considered two-body potential model can be used to predict the phase transition pressure in UX compounds provided the strength and hardness parameters in B1 and B2 phases are different.     

Electronic structure of cubic uranium compounds

Self-consistent cellular multiple scattering techniques and photoemission energy distribution curves obtained at 20<hv<80 eV are used to study the density of states of UN and US. The calculations are based on a model using a finite cluster of atoms in a condensed-matter-like boundary potential. The main results refer to the mixing of thes, p, d, andf-states of uranium into a valence and a conduction band. Thef-states form orbitals with the ligands, within the valence and conduction bands. In the nitride the amount off character in the valence band is only 0.3 electrons and thef electrons are in two resonant levels (of each spin) in the conduction band. Only the first of these levels is occupied for the local, alternate from atom to atom, majority spin. In the sulfide the amount off character in the valence band is 0.59 electrons and the rest of thef-levels are in a resonance state (of majority spin) at the beginning of the conduction band. The conduction band is mainly of localized uranium 6d character. The theoretical results compare favorably with the photoemission data reported here.     

Magnetization of uranium monopnictides in fields up to 40 T

Magnetization measurements at 1.3, 20 and 77 K on UN, UP, UAs and USb in fields up to 40 T are reported. While UN and USb have straight magnetization curves, UP and UAs show a number of magnetic transitions with extremely large hysteresis.     

Electronic structure of layered uranium compounds from photoemission spectroscopy

We present the photoemission results of two layered tetragonal compounds, the anti-ferromagnet UAsSe and ferromagnet USb₂. We observed intriguing electronic structure for both UAsSe and USb₂, in which relatively dispersive and narrow 5f bands are present. In the vicinity of the Fermi edge we found a very sharp photoemission peak with dispersion of several meV along the Γ to Z direction of the Brillouin zone. We also found a broader, hybridized f-character band with dispersion of several hundred meV along the Γ to X direction. Narrow and dispersive bands in these U-based magnetic materials are reminiscent of band magnetism as previously found in some transition metals.     

Low-temperature properties of Samarium monopnictides

SmP, SmAs, SmSb and SmBi order antiferromagnetically at Néel temperatures of 1.6, 1.8, 2.1 and 9 K, respectively. The crystal-field splittings _5/2 between the ₇ doublet and the ₈ quartet of theJ=5/2 ground state of the Sm³⁺ ion have been derived from caloric and magnetic measurements in the paramagnetic temperature range.     

Electrical resistivity of Sm monochalcogenides

The resistivity of mixed valence compounds has been computed in a two band Hubbard-like model. It is shown that there is a transition from a semiconductor to a metallic conductivity and that an intermediate valence can be found in both phases.     

Compressibility of the cerium monopnictides

Compressibilities of CeSb, CeAs and CeP have been obtained at room temperature from the pressure variation up to 41 kbar of the lattice parameters using neutron diffractometry.     

Magnetic properties of the cerium monochalcogenides

Single crystals of CeS, CeSe and CeTe have been investigated by means of measurements of the specific heat, the thermal expansion, the magnetic susceptibility and the magnetization at low temperatures. Crystal-field effects on some of these properties are used to derive the crystal-field splitting of the 4f electron ground state. It is found that chemical composition and crystal perfection strongly influence the magnetic properties of these compounds.     

Prediction of two-dimensional monochalcogenides: MoS and WS

Using density functional theory, we explore the possibility of two monolayer monochalcogenides, namely, MoS and WS. From the energetics, buckled and puckered structures are found to be more probable configurations. Our results on cohesive energy and phonon dispersion predict that the buckled structures of both MoS and WS are stable. On the other hand, while the puckered structure of WS clearly shows a dynamical instability, the same for MoS may have a stable configuration. Charge analyses predict ionic-like bonding in these systems. Density of states and band structure reveal a non-magnetic metallic nature for MoS in the stable configurations. However, for the buckled WS, our study predicts a non-magnetic semi-metallic nature. Further, semi-metal to indirect semiconductor transition has been observed for tensile strain of 5%, 6% and 8%.     

Propagation of ultrasonic waves in neptunium monochalcogenides

The ultrasonic attenuation and acoustic coupling constants due to phonon–phonon interaction and thermoelastic relaxation mechanisms have been studied for longitudinal and shear waves in B₁ structured neptunium monochalcogenides NpX (X: S, Se, Te) along 〈1 0 0〉 direction in the temperature range 100–300 K. The second and third order elastic constants (SOEC and TOEC) of the chosen monochalcogenides are also computed for the evaluation of ultrasonic parameters. The ultrasonic attenuation due to phonon–phonon interaction process is predominant over thermoelastic relaxation process in these materials. The ultrasonic attenuation in NpTe has been found lesser than other materials NpS, NpSe and GdY (Y: P, As, Sb and Bi). The semiconducting or semimetallic nature of neptunium monochalcogenides can be well understood with the study of thermal relaxation time. Total ultrasonic attenuation in these materials is found to be quadratic function of temperature. The nature of NpTe is very similar to semimetallic GdP. The mechanical and ultrasonic study indicates that NpTe is more reliable, perfect, flawless material.     

Electronic spectra of uranium tetrachloride clusters with electron-donor ligands

Electronic absorption spectra of nanoclusters of uranium tetrachloride are obtained experimentally and analyzed over a wide spectral range, from the visible to the IR. The structure of the long wavelength electronic absorption spectra is discussed in terms of the structure and electron-donor number of the attached ligand. Molecules of dimethyl sulfoxide (DMSO), hexamethyl phosphotriamide (HMPT), and water were used as ligands. The effect of the symmetry of the surroundings of the U⁴⁺ ion on the structure of the electronic spectrum is examined. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 182–187, March–April 2009.     

High-pressure behaviour and elastic properties of heavy rare-earth Gd monopnictides

Pressure-induced structural phase transition of gadolinium monopnictides GdX (X=As and Sb) has been studied theoretically using an inter-ionic potential theory. This method has been found quite satisfactory in case of the pnictides of rare-earth and describes the crystal properties in the framework of rigid-ion model. We have modified the ionic charge so that it may include the Coulomb-screening effect by the delocalization of f electron of the rare-earth ion. The anomalous structural properties of these compounds with many f electrons have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Gd ion with the p orbital of neighbouring pnictogen ion. Both the compounds are found to undergo from their initial NaCl (B₁) structure to body centered tetragonal (BCT) structure at high pressure and agree well with the experimental results. The BCT structure is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82–0.85. The nature of bonds between the ions is predicted by simulating the ion–ion (Gd–Gd and Gd–X) distance at high pressure. Elastic properties of these compounds have also been studied with their second-order elastic constants.     

Electronic structures and mechanical properties of uranium monocarbide from first-principles and calculations

The electronic structure, elastic constants, Poisson's ratio, and phonon dispersion curves of UC have been systematically investigated from the first-principles calculations by the projector-augmented-wave (PAW) method. In order to describe precisely the strong on-site Coulomb repulsion among the localized U 5f electrons, we adopt the local density approximation (LDA)+U and generalized gradient approximation (GGA)+U formalisms for the exchange correlation term. We systematically study how the electronic properties and elastic constants of UC are affected by the different choice of U as well as the exchange-correlation potential. We show that by choosing an appropriate Hubbard U parameter within the GGA+U approach, most of our calculated results are in good agreement with the experimental data. Therefore, the results obtained by the GGA+U with effective Hubbard parameter U chosen around 3 eV for UC are considered to be reasonable.