Features of Electronic Structure of Intermetallic Compounds CeNi<Subscript>4</Subscript>M (M = Fe,Co, Ni,Cu)

The evolution of the electronic structure of CeNi₄M (M = Fe, Co, Ni, Cu) intermetallics depending on the type of nickel substitutional impurity is explored. We have calculated band structures of these compounds and considered options of substituting one atom in nickel 3d sublattice in both types of crystallographic positions: 2c and 3g. The analysis of total energy self-consistent calculations has shown that positions of 2c type are more energetically advantageous for single iron and cobalt impurities, whereas a position of 3g type is better for a copper impurity. The Cu substitutional impurity does not change either the nonmagnetic state of ions or the total density at the Fermi level states. Fe and Co impurities, on the contrary, due to their considerable magnetic moments, induce magnetization of 3d states of nickel and cause significant changes in the electronic state density at the Fermi level.     

Electronic and optical properties of Fe<Subscript>2</Subscript>SiO<Subscript>4</Subscript> under pressure effect: ab initio study

We report first-principles studies the structural, electronic, and optical properties of the Fe₂SiO₄ fayalite in orthorhombic structure, including pressure dependence of structural parameters, band structures, density of states, and optical constants up to 30 GPa. The calculated results indicate that the linear compressibility along b axis is significantly higher than a and c axes, which is in agreement with earlier work. Meanwhile, the pressure dependence of the electronic band structure, density of states and partial density of states of Fe₂SiO₄ fayalite up to 30 GPa were presented. Moreover, the evolution of the dielectric function, absorption coefficient (α(ω)), reflectivity (R(ω)), and the real part of the refractive index (n(ω)) at high pressure are also presented.     

Electronic structure of the Np<Emphasis Type="Italic">MT</Emphasis> <Subscript>5</Subscript> (<Emphasis Type="Italic">M</Emphasis> = Fe,Co, Ni; <Emphasis Type="Italic">T</Emphasis> = Ga,In) series of neptunium compounds

Evolution of the electronic structure of the NpMGa₅ (M = Fe, Co, Ni) series of neptunium compounds, whose crystal structure is similar to that of the known family of Pu115 superconductors, was studied by the LDA + U + SO method. The calculations took into account both the strong electron correlations and the spin?orbit coupling in the 5f shell of neptunium. For the first time, the electronic structure was calculated for a hypothetical series of compounds in which gallium is replaced with indium. Parameters of the crystal structure of the given series were obtained using the relationship between the parameters of the crystal structure of the earlier-studied compounds PuCoGa₅ and PuCoIn₅. The analysis of the electronic structure and characteristics of neptunium ions calculated in the framework of the LDA + U + SO method showed that the neptunium ions in NpMIn₅ with M = Fe, Co, and Ni should have an electron configuration closer to f⁴, but a spin and magnetic characteristics close to those in NpMGa₅.     

Electronic Structure and Exchange Interactions in RNi<Subscript>4</Subscript>Co (R = Eu,Yb) Compounds

The electronic structure and the exchange interactions in EuNi₄Co and YbNi₄Co compounds have been calculated in terms of a theoretical approach with the inclusion of electronic correlations (LSDA + U method); the variants of substitution of cobalt ion for nickel in the 3d lattice in both types of crystallographic positions 2c and 3g are considered. The total energies obtained in self-consistent calculations show that individual cobalt impurities are more preferably arranged in position of the 3g type. A Co ion in RNi₄Co (R = Eu, Yb) is characterized by a significant magnetic moment, which leads to significant increase in the exchange interaction of Co and Ni ions in the 3d metal sublattice.     

Experimental Study and Analysis of Absorption Spectra of Ni<Superscript>2+</Superscript> Ions in Nickel Orthoborate Ni<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

The results of studies of the absorption spectra of nickel orthoborate Ni₃(BO₃)₂ in the range of electronic d–d-transitions are reported. The obtained data are analyzed in the framework of the crystal field theory. The Ni²⁺ ions are located in two crystallographically nonequivalent positions 2a and 4f with point symmetry groups C_2h and C₂, respectively, surrounded by six oxygen ions forming deformed octahedra. The absorption spectra exhibit three intense bands corresponding to spin-resolved transitions from the ground state of nickel ion ³A_2g (³F) to the sublevels of the ³T_2g (³F), ³T_1g (³F) and ³T_1g (³P) triplets split by the spinorbit interaction and the rhombic component of the crystal field. At temperatures below 100 K, the spectra exhibit a thin structure, in which phonon-free lines can be distinguished. Comparison of the calculated frequencies of the zero-phonon transitions with the experimental data allows estimating parameters of the crystal field acting on the nickel ions in the 2a- and 4f-positions, as well as the parameters of electrostatic interaction between the 3d electrons and spin-orbit interaction constants.     

High-frequency EPR of Cr<Superscript>2+</Superscript> ions in CdGa<Subscript>2</Subscript>S<Subscript>4</Subscript>

High-frequency broad-band (65–240 GHz) EPR is used to study impurity centers of bivalent chromium in a CdGa₂S₄ crystal. It is found that the EPR spectra correspond to tetragonal symmetry. The spin Hamiltonian H = βB · g · S + B ₂ ⁰ O ₂ ⁰ + B ₄ ⁰ O ₄ ⁰ + B ₄ ⁴ O ₄ ⁴ with the parameters B ₂ ⁰ =23659±2 MHz, B ₄ ⁰ =1.9±1 MHz, |B ₄ ⁴ |=54.2±2 MHz, g_‖=1.93±0.02, and g_⊥=1.99±0.02 is used to describe the observed spectra. It is concluded that chromium ions occupy one of the tetrahedrally coordinated cation positions.     

The Influence of Copper Impurity on the Electronic Structure and Optical Properties of TmNi<Subscript>5</Subscript> Compound

Investigations of the electronic structure and optical properties of TmNi_5–хСu_x (х = 0, 1, 2, 3) compounds were performed. Self-consistent calculations of the band spectrum have been performed in the local electron-spin-density approximation with a correction on strong electron interactions within the LSDA + U method. Total and partial densities of electron states associated with thulium, nickel, and copper atoms have been calculated. Optical conductivity, the behavior of which is interpreted for each compound taking into account the performed calculations, has been measured by the ellipsometry method in a wide wavelength range of 0.22–16 μm. Concentration dependences of plasma and relaxation frequencies of conduction electrons have been determined.     

Energy band structure and X-ray spectra of phenakite Be<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

The electronic structure of crystalline phenakite Be₂SiO₄ is investigated using x-ray emission spectroscopy (XES) (Be K _α XES, Si L _{2, 3} XES, O K _α XES) and x-ray absorption spectroscopy (XAS) (Be 1s XAS, Si 2p XAS, O 1s XAS). The energy band structure is calculated by the ab initio full-potential linearized augmented-plane-wave (FLAPW) method. The total and partial densities of states and the dispersion curves for the Be₂SiO₄ compound are presented. It is shown that the top of the valence band and the bottom of the conduction band of the Be₂SiO₄ compound are predominantly formed by the oxygen 2p states. According to the results obtained, the electron transition with the lowest energy supposedly can occur at the center of the Brillouin zone. The effective masses of electrons (0.5m _e ) and holes (3.0m _e ) for the Be₂SiO₄) compound are estimated.     

EPR and photoluminescence spectra of smooth CD<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films from T-10 tokamak: The effect of iron impurity

The electron and spin structure of thick smooth hydrocarbon CD _x films (“flakes”) with a high relative deuterium concentration of x ~ 0.5, redeposited from deuterium plasma discharge onto the walls of the vacuum chamber of the T-10 tokamak and containing ~1 at % of 3d-metal impurities due to erosion of the chamber walls, are studied using electron paramagnetic resonance (EPR) and photoluminescence (PL). The resulting spectra are compared for the first time to the EPR and photoluminescence spectra of polymer (soft) a-C:H(D) films (H(D)/C ~ 0.5), which are considered model analogues of smooth CD _x films. A certain similarity of the CD _x films with a-C:H films was found in the electronic structure of the valence band. At the same time, the differences in the EPR and photoluminescence spectra were observed due to the presence of 3d-metal impurities in the CD _x samples, contributing to the conversion of sp ³ → sp ² in the formation of films in the tokamak and upon heating and thermal desorption. An impurity of, presumably, 3d metals was detected for the first time by EPR in the a-C:H films in an amount of approximately 0.2 ppm, related to the evaporation of graphite.     

Comparative studies of microwave absorption in the singlet paramagnets HoVO<Subscript>4</Subscript> and HoBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in strong pulsed magnetic fields

Microwave absorption in the tetragonal singlet paramagnets HoVO₄ (zircon structure) and HoBa₂Cu₃O _x (x ≈ 6, layered perovskite structure) is studied and compared in pulsed magnetic fields up to 40 T at low temperatures. These paramagnets are characterized by a singlet-doublet scheme of the low-lying levels of the Ho³⁺ ion in a crystal field. In a magnetic field directed along the tetragonal axis, HoVO₄ exhibits resonance absorption lines at wavelengths of 871, 406, and 305 μm, which correspond to electron transitions between the low-lying levels of the Ho³⁺ ion in the crystal field. The positions and intensities of these absorption lines in HoVO₄ are well described in terms of the crystal-field formalism with the well-known interaction parameters. The absorption spectra of HoBa₂Cu₃O _x at a wavelength of 871 μm exhibit broad resonance absorption lines against the background of strong nonresonance absorption. The effects of low-symmetry (orthorhombic, monoclinic) crystal-field components, the deviation of a magnetic field from a symmetry axis, and various pair interactions on the absorption spectra of the HoVO₄ and HoBa₂Cu₃O _x crystals are discussed. Original Russian Text ? Z.A. Kazeĭ, V.V. Snegirev, M. Goaran, L.P. Kozeeva, M.Yu. Kameneva, 2008, published in Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2008, Vol. 133, No. 3, pp. 632–645.     

A theoretical investigation of structural,mechanical, electronic and thermoelectric properties of orthorhombic CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbI<Subscript>3</Subscript>

The structural, mechanical, electronic and thermoelectric properties of the low temperature orthorhombic perovskite phase of CH₃NH₃PbI₃ have been investigated using density functional theory (DFT). Elastic parameters bulk modulus B, Young’s modulus E, shear modulus G, Poisson’s ratio ν and anisotropy value A have been calculated by the Voigt–Reuss–Hill averaging scheme. Phonon dispersions of the structure were investigated using a finite displacement method. The relaxed system is dynamically stable, and the equilibrium elastic constants satisfy all the mechanical stability criteria for orthorhombic crystals, showing stability against the influence of external forces. The lattice thermal conductivity was calculated within the single-mode relaxation-time approximation of the Boltzmann equation from first-principles anharmonic lattice dynamics calculations. Our results show that lattice thermal conductivity is anisotropic, and the corresponding lattice thermal conductivity at 150 K was found to be 0.189, 0.138, and 0.530 Wm^?1K^?1 in the a, b, and c directions. Electronic structure calculations demonstrate that this compound has a DFT direct band gap at the gamma point of about 1.57 eV. The electronic transport properties have been calculated by solving the semiclassical Boltzmann transport equation on top of DFT calculations, within the constant relaxation time approximation. The Seebeck coefficient S is almost constant from 50 to 150 K. At temperatures 100 and 150 K, the maximal figure of merit is found to be 0.06 and 0.122 in the direction of the c-axis, respectively.     

Magneto-optical spectroscopy and optical detection of EPR spectra of Yb<Superscript>3+</Superscript> paramagnetic centers with cubic symmetry in single crystals <Emphasis Type="Italic">Me</Emphasis>F<Subscript>2</Subscript> (<Emphasis Type="Italic">Me</Emphasis> = Cd,Ca, Pb)

Cubic paramagnetic centers formed by Yb³⁺ impurity ions in fluorite-type crystals MeF₂ (Me = Cd, Ca, Pb) have been investigated using electron paramagnetic resonance, magnetic circular dichroism, magnetic circular polarization of luminescence, Zeeman splitting of optical absorption and luminescence lines, and optical detection of electron paramagnetic resonance. The g factors of the ²Γ₇ state in the excited multiplet ² F _5/2 of Yb³⁺ ions in Me F₂ crystals, the hyperfine interaction constant ¹⁷¹ A (¹⁷¹Yb) for the excited multiplet ² F _5/2 in the CaF₂ crystal, and the energies and symmetry properties of all energy levels of Yb³⁺ ions in MeF₂ crystals are determined. The crystal-field parameters for the crystals under investigation are calculated.     

Charge state of a transition metal impurity in II–VI semiconductors

The results of calculating the electronic structure of semiconductor compounds A^IIB^VI: 3d(A = Zn; B = S, Se, Te; 3d = Sc-Cu) at a low content of 3d impurities are discussed. The excess charge of an impurity ion with respect to the charge of the zinc ion is determined for the whole series of 3d impurities. It is found that the excess charge gradually varies from +0.6|e| for the scandium impurity to ?0.2|e| for the copper impurity. Photoionization of an impurity ion is simulated by adding a hole or an electron to the impurity center. The added charge is redistributed between the impurity ion and its nearest neighbors, thus decreasing or increasing the total excess charge of the impurity center by a magnitude of ～ 0.2|e|.     

Energy Band Structure and Optical Properties of LiNaSO<Subscript>4</Subscript> Crystals

The energy band structure of a LiNaSO₄ has been calculated within the framework of density functional theory for space group P31c. It has been established that bandgap width E_g in the GGA approximation is 5.49 eV. The valence band top is generally formed of oxygen p-electrons, while the conduction band bottom is composed of lithium and sodium s-states. The effect of the cationic substitution Na → K → Rb → NH₄ on the electron structure of LiBSO₄ group crystals is considered. Based on the calculated dielectric functions, the spectral dependences of the refractive indices and extinction coefficient of a crystal were calculated and compared with experimental data.     

Study of absorption spectra of Er<Superscript>3+</Superscript> in KTaO<Subscript>3</Subscript> crystals

The first results of the study of optical absorption spectra of KTaO₃: Er³⁺ crystals are presented. In the 350–660-nm region, lines are observed deriving from intraconfigurational electronic transitions from the ⁴ I _15/2 ground state to levels of the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, ⁴ F _7/2, ⁴ F _5/2(⁴ F _3/2), ² G _9/2, and ⁴ G _11/2 excited states of the Er³⁺ ions. A comprehensive study of transitions to the ⁴ F _9/2, ⁴ S _3/2, ² H _11/2, and ⁴ F _7/2 levels at 77 K is carried out. The number of lines observed for the above transitions fits the theoretically possible number for ?-? electronic transitions in Er³⁺ ions in the cubic crystal field. In the case of a differently charged substituted ion, this situation occurs only under nonlocal impurity charge compensation. The energies of the excited state levels for the transitions under study are determined.     

Electronic structure and correlations of vitamin B<Subscript>12</Subscript> studied within the Haldane-Anderson impurity model

We study the electronic structure and correlations of vitamin B₁₂ (cyanocobalamine) by using theframework of the multi-orbital single-impurity Haldane-Anderson model of atransition-metal impurity in a semiconductor host. The parameters of the effectiveHaldane-Anderson model are obtained within the Hartree-Fock (HF) approximation. Thequantum Monte Carlo (QMC) technique is then used to calculate the one-electron andmagnetic correlation functions of this effective model. We observe that new states forminside the semiconductor gap found by HF due to the intra-orbital Coulomb interaction atthe impurity 3d orbitals. In particular, the lowest unoccupiedstates correspond to an impurity bound state, which consists of states from mainly the CNaxial ligand and the corrin ring as well as the Co e_g-like orbitals. We alsoobserve that the Co?(3d) orbitals can develop antiferromagneticcorrelations with the surrounding atoms depending on the filling of the impurity boundstates. In addition, we make comparisons of the HF+QMC data with the density functionaltheory calculations. We also discuss the photoabsorption spectrum of cyanocobalamine.     

Magnetic structure of the Sr<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>4</Subscript>Cl<Subscript>2</Subscript> two-subsystem antiferromagnet according to nuclear quadrupole resonance data

The magnetic structure of the Sr₂Cu₃O₄Cl₂ two-subsystem antiferromagnet is studied by the nuclear quadrupole resonance (NQR) method on the ^{63, 65}Cu and ³⁵Cl nuclei. The resonance spectrum above T _N2 = 40 K is determined by the Zeeman splitting of the levels of the ^{63, 65}Cu nuclei of the copper atoms at the Cu1 site with the first-order quadrupole perturbation. The magnetic field on the copper nuclei is equal to 93 kOe. The spectrum below n is significantly different: it includes a low-frequency part, which is associated with the ordering of the second magnetic subsystem Cu2. The splitting of the NQR lines of ³⁵Cl is observed above and below T _N2. This fact indicates the ferromagnetic ordering of the moments of the Cu1 subsystem, which are located along the c axis of the crystal, and makes it possible to determine the direction of the magnetic field on Cu1 copper as (110).     

Ab initio calculations of B<Subscript>2</Subscript> type RHg (R = Ce,Pr, Eu and Gd) intermetallic compounds

Spin polarized ab initio calculations have been carried out to study the structural, electronic, elastic and thermal properties of RHg (R = Ce, Pr, Eu and Gd) intermetallic compounds in B₂ structure. The calculations have been performed by using both generalized gradient approximation (GGA) and local spin density approximation (LSDA). The calculated value of lattice constant (a ₀) for these compounds with GGA is in better agreement with the experimental data than those with LSDA. Bulk modulus (B), first-order pressure derivative of bulk modulus and magnetic moment (μ _B ) are also presented. The energy band structure and electron density of states show the occupancy of 4f states for light as well as heavy rare earth atom. The elastic constants are predicted from which all the related mechanical properties like Poisson’s ratio (σ), Young’s modulus (E), shear modulus (G _H ) and anisotropy factor (A) are calculated. The ductility or brittleness of these compounds is predicted from Pugh’s rule (B/G _H ) and Cauchy pressure (C ₁₂ ? C ₄₄). The Debye temperature (θ _D ) is estimated from the average sound velocity, which have not been calculated and measured yet.     

Nuclear spin resonance of <Superscript>53</Superscript>Cr in ferromagnetic CuCr<Subscript>2</Subscript>S<Subscript>4</Subscript>: Sb

The influence of variable valence on NSR spectra of ⁵³Cr nuclei in ferromagnetic CuCr_2?xSb_xS₄ (x = 0, 0.02, 0.07) at T = 77 K is considered. For quadrupole nuclei in locally anisotropic positions, the effects of variable valence result in averaging of not only the resonance frequency but also of the quadrupole and magnetic anisotropy constants. The significant difference between the experimental and calculated values of these constants indicates the important role of the intrinsic electronic contribution to the anisotropy of hyperfine fields of compounds containing Cr⁴⁺ ions. Additional lines caused by intrinsic and induced defects in the structure are observed in the spectra of doped and undoped compounds.