Electronic structure of Yb, Ag, and Cu in the heavy-fermion system YbCu5−x Agx

The method of shifts of x-ray diffraction lines is used to study the electronic structure (the populations of 4f states in Yb, 5s states in Ag, and 4s states in Cu) in the heavy-fermion system YbCu_5?x Ag_x (0≤x≤1, T=300 K for Cu and Ag and 77, 300, and 1000 K for Yb). In the cubic phase (AuBe₅-type structure), Yb is shown to exist in the state with a noniteger valence whose magnitude is independent of the composition and is equal to $\bar m_{cub} = 2.91 \pm 0.01$ . At x<0.125, in the two-phase region (a mixture of cubic AuBe₅-type and hexagonal CaCu₅-type phases), the magnitude of m decreases with decreasing x. Based on the experimental values of m in the cubic and hexagonal phases in the two-phase region, the valence of Yb in the hexagonal phase was found to be $\bar m_{hex} = 2.71 \pm 0.04$ . With increasing temperature in the range of 77–1000 K, a linear decrease in m for the samples from the cubic-phase field and a linear increase in m for the samples from the two-phase field is observed. At T=1000 K, the valence of Yb in the cubic and hexagonal phases is virtually the same: m _cub=2.83±0.02 and m _mix=2.78±0.02. The cubic phase exhibits a composition-independent increase in the population of 5s states of Ag (in comparison with the metal) $\overline {\Delta n} _{5s} (Ag) = 0.69 \pm 0.07$ electron/atom and a simultaneous linear increase in Δn _4s (Cu) from about 0.1 electron/atom for x=1 to about 0.3 electron/atom for x=0.2. The difference in the behavior of the effects of Δn _s for Cu and Ag is explained by the specific features of the crystal structure of YbCu_5?x Ag_x. It follows from the analysis of microscopic and macroscopic properties that YbCu_5?x Ag_x is a system with an intermediate valence and, correspondingly, the increase in the effective mass of electrons in it is related to the shift of the 4f-electron level to the Fermi level (delocalization). The effect of the increase in the population of s states in the partners of Yb is explained by the fact that, upon the transition into the state with an intermediate valence, the 4f electron of Yb is hybridized with s electrons of neighboring atoms of Ag and Cu rather than with the electrons of Yb itself.     

Martensitic transformation in La1−x Yb x Ag1−y In y

The structural phase transformation of La_1–x Yb _x Ag_1–y In _y has been studied on single crystals by low temperature Laue-technique. The martensitic transformation in this pseudobinary intermetallic alloy has to be characterized as a weak orthorhtombic distortion of a single I centered unit cell (c/a1.04;a/b1.006) and a collective slipping or twinning of these cells that gives a fixed orientation between the remaining cubic room temperature structure and the martensitic phase. Above room temperature exists an order-disorder transformation from the CsCl-B2 structure to an at room temperature metastable W-A2 structure. There is no dramatic change in the physical properties of this alloy by substituting La by Yb, so we may approximate our results to LaAg_1–y In _y .This paper is dedicated to Prof. Dr. S. Methfessel on the occasion of his 60^th birthday     

Thermal conductivity of the “light” heavy-fermion compound YbIn0.7Ag0.3Cu4

This paper reports on the electrical resistivity and thermal conductivity of polycrystalline YbIn_0.7Ag_0.3Cu₄ at temperatures from 4.2 to 300 K, which exhibits, at T _v , a continuous isostructural first-order phase transition from a Curie-Weiss paramagnet with localized magnetic moments (for T>T _v ) to a Pauli paramagnet in a nonmagnetic Fermi liquid state with the Yb ion in a mixed valence state (for T<T _v ). It is shown that for T<T _v , the Lorenz number behaves in accordance with the theoretical model developed for heavy-fermion materials, while for T>T _v , it acquires the value typical of standard metals.     

The electronic structure of the mixed 5f system UC x N1−x

We present results of electronic structure calculations for UC _x N_1–x obtained with the relativistic Korringa-Kohn-Rostocker Greens function (RKKR-GF) method. While on the anion sites the disorder is treated within the Coherent Potential Approximation (CPA) the small change in the cation potential upon alloying is accounted for in the averaget-matrix approximation (ATA). The presence of strong local spin fluctuations forx0.6 restricts our treatment to the carbon rich phase, and even there we find that the observed linear specific heat coefficient is much enhanced over the bandstructure value. The computed X-ray photoemission spectra vary smoothly with composition the main change consisting in the melting away of the side peak at –3 eV binding energy seen in pure UC with the adjunction of nitrogen.     

Positron annihilation studies on the electronic structure of Pd−Ag−H system

Angular Correlation of Annihilation Radiation (ACAR) is shown to be useful to examine the electronic structure of -phase Pd_1–y Ag _y H _x system. Hydrogen absorption by Pd_1–y Ag _y alloys results in the increase of both nearly free andd-localized electron numbers in compliance with the KKR-CPA calculation outcomes. The investigation of -phase systems, PdH _x hydrides as well as Pd_1–y Ag _y H _x materials, failed because of a high concentration of lattice defects.     

Experimental and theoretical investigations of the Knight shift of Pd and Ag in the alloy system Ag x Pd1−x

The Knight shift of Pd in Ag _x Pd_1–x has been determined for concentrationsx0.2. In full accordance with the expectations based on the behaviour of the magnetic susceptibility, it was found that the Knight shift of Pd is rapidly reduced in magnitude by adding Ag to Pd. To allow for a detailed interpretation of this finding, we have performed Korringa-Kohn-Rostoker coherent potential approximation (KKR-CPA) band structure calculations for Ag _x Pd_1–x . These calculations clearly demonstrate that the decrease in spin susceptibility with increasingx is accompanied with a decrease in core polarization. In contrast to Pd, the negative Knight shift of Ag on the Pd-rich side of the system is caused by the valence band contribution, as it is demonstrated by our calculations. This is caused by an intersite effect in analogy to the transferred hyperfine field found for non-magnetic elements dissolved in a magnetic host.     

Specific features of the electronic structure and spectral properties of NdNi5 − x Cu x compounds

The spectral properties of the intermetallic compounds NdNi_{5 ? x} Cu _x (x = 0, 1, 2) have been studied using optical ellipsometry in the wavelength range 0.22–16 μm. It has been established that substitution of copper atoms for nickel leads to noticeable changes in the optical absorption spectra, plasma frequencies, and relaxation frequencies of conduction electrons. Spin-polarized calculations of the electronic structure of these compounds have been performed in the local spin density approximation allowing for strong electron correlations (LSDA + U method) in the 4f shell of the rare-earth ion. The calculated electron densities of states have been used to interpret the experimental dispersion curves of optical conductivity in the interband light absorption region.     

Theory of the electronic structure of Ga1-yInyNxAs1−x and related alloys

Abstract

We present a quantitative k.P Hamiltonian which describes analytically the composition dependence of the energy gap, interband momentum matrix element, band edge effective masses and conduction band dispersion of GaN_XAs_1?x alloys for low N concentrations (x < ～ 0.05). The model has been confirmed using an sp³s? tight-binding Hamiltonian whose results agree well both with experiment and with previous pseudopotential calculations. The model should be of wide use to guide the future development of this material system and its applications.     

Electrical properties and electronic structure of Cu1−xZnxInSe2 and Cu1−xZnxInS2 single crystals

Temperature dependence of the electrical conductivity of CuInS₂–ZnIn₂S₄ and CuInSe₂–ZnIn₂Se₄ solid solutions possessing n-type conductivity has been studied. It has been established that when the temperature decreases down to ~100 to 27 K, the hopping mechanism of electrical conductivity with a variable jumping length between localized states positioned in a narrow energy band near the Fermi level becomes dominant. The main parameters of the hopping conductivity have been determined. At higher temperatures (150–300 K), in the CuInSe₂–ZnIn₂Se₄ single crystals containing 15 and 20 mol% ZnIn₂Se₄ the thermally activated conductivity with activation energy of 0.018 and 0.04 eV, respectively, is detected. Among the CuInSe₂–ZnIn₂Se₄ single crystals, samples with 5 and 10 mol% ZnIn₂Se₄ were found to be close to degenerate semiconductors. Temperature dependences of the electrical conductivity of CuInS₂–ZnIn₂S₄ single crystals are described by a more complicated function that may indicate a competition of several conduction mechanisms in these compounds. For the CuInS₂–ZnIn₂S₄ solid solutions, X-ray photoelectron core-level and valence-band spectra have been measured for both pristine and Ar⁺ ion-bombarded surfaces. Our results indicate that the Cu_1−xZn_xInS₂ single-crystal surfaces are sensitive to Ar⁺ ion-bombardment. Additionally, for the Cu_1−xZn_xInS₂ crystal with the highest ZnIn₂S₄ content, namely 12 mol% ZnIn₂S₄, the X-ray emission bands representing the energy distribution of the Cu 3d, Zn 3d and S 3p states have been measured and compared on a common energy scale with the X-ray photoelectron valence-band spectrum.     

Concentration-dependent crystal structure,elastic constants and electronic structure of Zr x Ti1−x alloys under high pressure

The physical properties of ZrxTi1-x（x=0.0, 0.33, 0.5, 0.67, 0.75 and 1.00） alloys were sinmlated by virtual crystal approximation （VCA） methods which is generally used for disordered solid solutions modeling. The elastic constant, electronic structure and thermal Equation of state （EOS） of disor- dered ZrxTi1-x alloys under pressure are investigated by plane-wave pseudo-potentia1 method. Our simulations reveal increasement of variations of the calculated equilibrium volumes and decrease- ment of Bulk modulus as a function of the alloy compositions. Lattice parameters a and c of alloys with differentZr concentrations decrease linearly with pressure increasing, but the c/avalues are increasing as pressure increases, indicating no phase transitions under pressure from 0 GPa to 100 GPa. The elastic constants and the Bulk modulus to the Shear modulus ratios （B/G） indicate good ductility of Zr, Zr0.33 Ti0.67 Zr0.5Ti0.5, Zr0.75Ti0.25 and Ti, but the Zr0.67Ti0.33 alloy is brittle under 0 K and 0 GPa. The metallic behavior of these alloys was also proved by analyzing partial and total DOS.     

Electronic structure of Rh, Pt, In, and Sn in the mixed-valence systems Eu(Rh1−x Ptx)2 and U(In1−x Snx)3

The electronic structure of Rh, Pt, In, and Sn in the mixed-valence systems Eu(Rh_1−x Pt_x)₂ and U(In_1−x Sn_x)₃ has been studied by the x-ray K line-shift method. It has been found that the occupation of the Rh 4d-shell in Eu(Rh_1−x Pt_x)₂ is higher than that in the metal, and that it grows with decreasing Eu valence (i.e., with increasing 4f-shell occupation). The electronic structure of Pt, In, and Sn in Eu(Rh_1−x Pt_x)₂ and U(In_1−x Sn_x)₃ does not depend on the Eu and U valence and is practically the same as in the metals. These features in the electronic structure of Rh, Pt, In, and Sn in Eu(Rh_1−x Pt_x)₂ and U(In_1−x Sn_x)₃ suggest that the electron released in the f ⁿ → f ⁿ −1+e transitions, rather than transferring to the common conduction band, remains localized at the Eu and U atoms. Fiz. Tverd. Tela (St. Petersburg) 41, 1529–1531 (September 1999)     

Optical spectroscopy and electronic structure of compounds HoNi5 − x Al x (x = 0, 1, 2)

The optical properties of the compounds HoNi_{5 ? x} Al _x (x = 0, 1, 2) have been investigated using the ellipsometric method in the wavelength range from 0.22 to 16 μm. The electronic structure of these intermetallic compounds has been calculated in the local electron-spin density approximation with the correction for strong electronic interactions in the 4f shell of the holmium ions. The experimental dispersion dependences of optical conductivity in the region of interband light absorption have been interpreted based on the results of the calculation of the electron density of states. The plasma and relaxation frequencies of electrons have been determined.     

The electronic structure,elastic and optical properties of Cu2ZnGe(SexS1 − x)4 alloys: density functional calculations

The electronic structure, elastic and optical properties of Cu₂ZnGe(Se_xS_{1 ? x})₄ alloys are systematically analysed using first-principles calculations. The lattice parameters agree well with the theoretical and experimental values which are searched as complete as possible indicating our calculations are reliable. The elastic properties are investigated first and are compared with the similar compounds CZTS and CZTSe due to the unavailable experimental data currently. The variation of the optical properties caused by the increase of Se/S ratio is discussed. The static optical constants are calculated and the corrected values are also predicted according to the available experimental data.     

Calculation of the electronic structure and hyperfine fields for Fe1 − x Co x B and (Fe1 − x Co x )2B compounds by the Korringa-Kohn-Rostoker method

The magnetic properties of Fe_{1 ? x} Co _x B and (Fe_{1 ? x} Co _x )₂B disordered compounds were investigated using first-principles calculations of the electronic structure in the framework of the density functional theory with the Korringa-Kohn-Rostoker method. The concentration dependences of the magnetic moments and the electron density were calculated for the Fe_{1 ? x} Co _x B solid solutions. The results obtained were used to analyze in detail and to interpret the transition from a magnetic phase to a nonmagnetic phase, which was previously revealed from the experiments in the compounds under investigation. The performed analysis of the calculated hyperfine fields induced by the electronic shells at the iron and cobalt atoms in the (Fe_{1 ? x} Co _x )₂B borides made it possible to explain the experimentally observed magnetic anisotropy.     

Electron spin resonance study of the dynamic magnetic susceptibility of CuO, Cu1−x Zn x O, and Cu1−x Li x O single crystals

Results are presented of studies of the dynamic magnetic susceptibility of CuO, Cu_1?x Zn _x O (x ≈ 1.5%), and Cu_1?x Li _x O (x ≈ 1%) single crystals. The orientational dependence of the ESR spectra was investigated at room temperature. The results for CuO are analyzed using a model of a quasi-one-dimensional antiferromagnet (S = 1/2) with anisotropic exchange interaction between Cu²⁺ spins in the chains and exchange coupling between the chains allowing for one-dimensional spin diffusion and spinon excitations. The estimated line width is of the same order of magnitude as the experimental data. Substituting Cu with Zn scarcely alters the spin dynamics of the Cu²⁺ ions, as in weakly diluted magnets. Lithium doping substantially increases the ESR line width and this is attributed to excess holes forming rapidly relaxing spin complexes with copper ions.     

Rotational structure of the origin band in the 1A′ ←X1σ+ electronic transition of C4H− and C4D−

The rotational structure of the origin band for the ¹A′←X¹σt⁺ electronic transition, lying just below the electron affinity of C⁴H, was recorded by means of a two-colour resonant photodetachment technique. This allowed a determination of the rotational constants in the X¹σt⁺ ground and ¹A′ dipole bound excited state. The low lying A²II excited state of C⁴H is inferred to be the parent of the dipole bound state. The excited electronic state is deduced to have a nonlinear planar structure whereas the ground is linear according to the spectral analysis. The rotational constants have been obtained: B′; = 0.1552(2)cm^?1 for the X¹σt⁺ state, and A′ = 30.73(1), B′ = 0.1587(2), C′ = 0.1581(2)cm^?1 for the ¹A′ state.     

Structural and electronic properties of GaN x As1−x alloys

The structural and electronic properties of cubic GaN _x As_1−x with N-concentration varying between 0.0 and 1.0 with step of 0.25 were investigated using the full potential–linearized augmented plane wave (FP-LAPW) method. We have used the local density approximation (LDA) and the generalized gradient approximation (GGA) for the exchange and correlation potential. In addition the Engel-Vosko generalized gradient approximation (EVGGA) was used for the band-structure calculations. The structural properties of the binary and ternary alloys were investigated. The electronic band structure, total and partial density of states as well as the electron charge density were determined for both the binary and their related ternary alloys. The energy gap of the alloys decreases when we move from x=0.0 to 0.25; then it increases by a factor of about 1.8 when we move from 0.25 to 0.5, 0.75 and 1.0 using EVGGA. For both LDA and GGA moving from x=0.0 to 0.25 causes the band gap to close, showing the metallic nature of the GaN_0.25As_0.75 alloy. When the composition of N moves through x=0.25, 0.5, 0.75 and 1, the band gap increases.     

Influence of the composition on electrical properties of low-temperature ionic conductors in the Cu1 ? x Ag x GeAsSe3 system

The chalcogenides Cu_{1 ? x} Ag _x GeAsSe₃ (x = 0.5, 0.8, 0.9) have been synthesized and their electrical properties have been studied at low temperatures. Compounds of this type are electron-ionic conductors with a mixed character of conduction. It has been shown that the substitution of copper atoms for a part of silver atoms in the AgGeAsSe₃ compound leads to a decrease in the total conductivity, a decrease in the fraction of ionic component of the conductivity, a significant increase in the polarization times, an increase in the temperature of the onset of a noticeable contribution (as compared to the electron contribution) of the ionic transport, and a decrease in the activation energy of carriers.