Electronic structure of α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>: Ab initio simulations and comparison with experiment

Al₂O₃ films 150 Å thick are deposited on silicon by the ALD technique, and their x-ray (XPS) and ultraviolet (UPS) photoelectron spectra of the valence band are investigated. The electronic band structure of corundum (α-Al₂O₃) is calculated by the ab initio density functional method and compared with experimental results. The α-Al₂O₃ valence band consists of two subbands separated with an ionic gap. The lower band is mainly formed by oxygen 2s states. The upper band is formed by oxygen 2p states with a contribution of aluminum 3s and 3p states. A strong anisotropy of the effective mass is observed for holes: m _h⊥ ^* ≈ 6.3m ₀ and m _h‖ ^* ≈ 0.36m ₀. The effective electron mass is independent of the direction m _e‖ ^* ≈ m _e⊥ ^* ≈ 0.4m ₀.     

Development of the method for low-temperature investigations of HTSC systems on an X-ray electron magnetic spectrometer

Peculiarities of the chemical structure of bulk polycrystalline samples of the high-temperature superconductors Bi₂Sr₂CaCu₂O₈, BiSrCaCu₂O_5.5, BiSrCaCu₃O₈, and YBa₂Cu₃O_{7 ? δ} have been investigated in detail at room and superconducting temperatures on an X-ray electron magnetic spectrometer equipped with an attachment for low-temperature studies. It is shown that covalent bonding is formed at a superconducting temperature between copper and oxygen due to Cu²⁺ ions. Due to the enhancement of the d(Cu)–p(O) hybridization of copper and oxygen electrons in the superconducting state, the d-electron density increases near E _F. The occurrence of additional peaks in the O1s and Sr3d (Ba3d) spectra after transition of the system to the superconducting state indicates changes in the nearest environment of O and Sr (Ba) atoms, in particular, the transition of Sr atoms to a higher oxidation state.     

Investigations of the interlayer coupling in high-<Emphasis Type="Italic">T</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript> cuprates

Low-field magnetizationM(H) measurements can be used to probe the nature of the screening currents and the interlayer coupling in high-T _c cuprates. Here we compare theM(H) behaviour of single crystals of Bi₂Sr₂CaCu₂O₈ and fully oxygenated and oxygen reduced YBa₂Cu₃O_7??. In YBa₂Cu₃O₇, theM(H) behaviour is consistent with anisotropic 3D superconductivity whilst in Bi₂Sr₂CaCu₂O₈, the surface screening currents are strongly affected by the presence of vortices, implying that the CuO₂ planes are coupled via a weak Josephson interaction. In oxygen-deficient YBa₂Cu₃O_6.7 (T _c =63K), theM(H) behaviour at low temperatures is similar to that found for Bi₂Sr₂CaCu₂O₈, implying that the removal of oxygen from the chains has resulted in a dimensional crossover of the superconducting state in YBa₂Cu₃O_7??. As the temperature approachesT _c , the 3D behaviour is eventually restored as thec-axis coherence length ξ _c becomes comparable with the interlayer spacingd.     

Raman spectroscopy of crystalline,glassy, and molten states of lead diborate

Polarized Raman spectra of single crystals of lead diborate, PbB₄O₇ (PBO), are studied in detail at 300 K. The TO-, LO-, and IO-phonon lines of the A ₁, A ₂, B ₁, and B ₂ symmetries in the Raman spectra of this compound are assigned. Changes in the Raman spectra of the internal vibrations of boron–oxygen complexes upon transition from the crystalline to the glassy and the molten states of PBO are observed. On the basis of the obtained results, the regularities in the formation of boron–oxygen complexes in glasses, melts, and crystals of the PbO · 2B₂O₃, SrO · 2B₂O₃, and Li₂O · 2B₂O₃. diborate compositions are analyzed.     

Branches of zero sound excitations in asymmetric nuclear matter: The dependence on density

Results from calculating zero sound excitations in isospin asymmetric nuclear matter are presented. A polarization operator constructed in the random phase approximations is used in the calculations. Three branches of the complex solutions ω_sτ(k), τ = p,n,np are presented. The type of branch depends on that of the considered branch damping. An imaginary part of the solution corresponds to the damping of collective excitations due to mixing with the background of noninteracting (1) proton particle–hole pairs (ω _sp (k)), (2) neutron particle–hole pairs (ω _sn (k)), and (3) both proton and neutron particle–hole pairs (ω _snp (k)). The behavior of the solutions upon variations in density depends on the value of the asymmetry parameter.     

Structural and compositional heterogeneities in liquid aluminosilicate: insight from a grain structure model

Network structure as well as structural and compositional heterogeneities in aluminosilicate (Al₂O₃-2SiO₂) under compression is investigated by analysis and visualization of simulation data. Structural and compositional heterogeneities are clarified through analysis of topology structure and size distribution of TO _x -clusters (T = Si, Al; x = 3, 4, 5, 6) as well as OT _y -clusters (y = 2, 3, 4). The TO _x -cluster can be considered as TO _x -grains. It appears that the structure of aluminosilicate is the mixture of TO _x -grains with a different short-range order structure and this is the origin of structural heterogeneity. Regarding their composition, the OSi _y - and OAl _y -clusters can be considered as silica- and alumina-grains respectively, and the structure of aluminosilicate can thus be considered to be formed from silica- and alumina-grains. This results in compositional heterogeneity. Moreover, the degree of polymerization and polyamorphism as well as dynamic heterogeneity is also discussed in detail.     

Synthesis,structure, and properties of BIFENBVOX

Solid solutions Bi₄V_2-x Fe _x/2Nb _x/2O_11-δ (х?=?0.05–1.0) and Bi₄V_2-х-y Fe _x Nb _y O_11–δ (with fixed x or y?=?0.2 and variable х or y?=?0.2–0.5 with step 0.1) were synthesized by the standard ceramic technology in the temperature range 773–1113 K and by mechanochemical activation method using Bi₂O₃, V₂O₅ Fe₂O₃, and Nb₂O₅ oxides as initial compounds. The formation of solid solutions was studied. Ranges of stability and temperature values of phase transitions for different polymorphous modifications were defined using dylatometric and thermo gravimetric studies. The morphology and the local chemical composition of the ceramic samples were studied. Samples with concentration of dopants x?>?0.3 contain two phases; both major and impurity phases are solid solutions of the BIFENBVOX type although the dopants atoms distribution between them is random. The thermal expansion coefficients (TEC) were measured. The electrical conductivity of ceramic samples was investigated in a wide range of temperatures. The highest conductivity values among the studied solid solutions are observed for the sample with a small amount of dopants x?=?0.25.     

Hyperfine nuclear interaction at copper lattice sites of high-temperature superconductors studied by <Superscript>61</Superscript>Cu(<Superscript>61</Superscript>Ni) Mössbauer emission spectroscopy

Mössbauer emission spectroscopy on the ⁶¹Cu(⁶¹Ni) isotope has been used to determine the quadrupole coupling constant C(Ni) and magnetic induction B(Ni) for the ⁶¹Ni²⁺ probe at copper sites in Cu₂O, CuO, La_{2 ?x}Ba_xCuO₄, Nd_2?xCe_xCuO₄, RBa₂Cu₃O₆, and RBa₂Cu₃O₇ (R=Y, Nd, Gd, Yb). The compounds containing divalent copper were found to exhibit linear C(Ni) vs. C(Cu) and B(Ni) vs. B(Cu) relations [C(Cu) and B(Cu) are the quadrupole coupling constant and magnetic induction for the ⁶³Cu probe, respectively, found by NMR], which is interpreted as an argument for the copper being in divalent state. The deviation of the data points corresponding to the Cu(1) sites in RBa₂Cu₃O₆ and RBa₂Cu₃O₇ from the C(Ni) vs. C(Cu) straight line may be due either to the copper valence being other than 2+ (in the RBa₂Cu₃O₆ compounds) or to the principal axes of the total and valence electric field gradient being differently oriented (in the RBa₂Cu₃O₇ compounds).     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Electron paramagnetic resonance of Er<Superscript>3+</Superscript> ions in a polycrystalline α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The EPR spectra of rare-earth Er³⁺ ions in a polycrystalline corundum α-Al₂O₃ synthesized by the sol-gel technology were revealed. It is shown that the EPR spectra belong to the Er³⁺ ions in the ground state corresponding to the lower Stark sublevel of the ⁴ I _15/2 term and can be described by the spin Hamiltonian of axial symmetry with an effective spin S = 1/2 and the g tensor with components g _‖ = 12.176 and g _⊥ = 4.14. The average value of the g tensor (〈g〉 = 6.82) corresponds to the Γ₇ state in a cubic field. Erbium is assumed to substitute for aluminum in the Al₂O₃ corundum crystal. The local symmetry C ₃ of the Al³⁺ ion remains despite the pronounced expansion of the lattice around the Er³⁺ ion.     

Magneto-optical properties of Dy<Superscript>3+</Superscript> in oxide glasses: The origin of the magneto-optical activity of <Emphasis Type="Italic">f-f</Emphasis> transitions and its anomalous temperature dependence

The temperature dependence of the absorption spectra and magnetic circular dichroism due to f-f transitions from the ⁶ H _15/2 to ⁶ F _5/2 and ⁶(F _7/2 + H _5/2) states in the Dy³⁺ ion in (Dy₂O₃-P₂O₅-SiO₂-GeO₂) and (Dy₂O₃-La₂O₃-Al₂O₃-B₂O₃-SiO₂-GeO₂) glasses and the temperature dependence of the Faraday effect were studied. The temperature dependence of the Faraday effect caused by f-d transitions was found to differ from that of the magnetic circular dichroism due to f-f transitions. It was shown that f-f transitions occur preferentially in Dy³⁺ ions associated into clusters. The origin of the paramagnetic magneto-optical activity of f-f transitions was analyzed. It was shown that the contributions to this activity can differ in value and sign and that the ratio between these contributions depends on the transition type. In some cases, this difference results in an anomalous temperature dependence of the magneto-optical activity.     

Initiation of combustion of a hydrogen-air mixture with ozone impurity by UV laser radiation

The ignition kinetics of hydrogen-air mixtures with a small amount (0.5%) of ozone that are exposed to laser radiation with wavelength λ _I = 248.4 nm is analyzed. The formation of excited O(¹ D) atoms and O₂(a ¹Δ _g ) molecules due to O₃ molecule photodissociation is shown to greatly intensify the chain reactions and noticeably decrease the induction period and ignition temperature compared with the case when the radiation is absent even if the radiation energy applied to the gas is low, E _s = 0.5?1.0 eV per O₃ molecule. The efficiency of such a way of combustion initiation is much higher than at local heating of the medium by laser radiation but, at the same time, is considerably lower than the efficiency of the method based on excitation of O₃ molecule asymmetric oscillations.     

Applications of a unique group embedding of internal symmetry groups andSU(2): spin-extensions for G2 and for the Sp(6)-Trion model

A recently proposed method of embeddingSU (2) and an internal symmetry groupG into a bigger groupG is applied to construct a spin extension ofG ₂ andSp (6). BecauseG ₂ andSp (6) possess a generalized quark model the embedding group can be proved to be unique and to be given bySp (14) resp.O (12) forG ₂ resp.Sp (6). For a particle classification splittings are calculated and tabulated forSp (14) ↓G ₂ xSU (2) andO (12) ↓Sp (6) xSU (2). The identification of low dimensional irreducible representations ofO (12) is quite satisfactory whereas an unreasonable number of unobserved particles are needed to fill up the supermultiplets of the spin extensionSp (14) of G₂.     

Theory of the microstructure of disordered <Emphasis Type="Italic">AA</Emphasis>′BO<Subscript>3</Subscript> and <Emphasis Type="Italic">ABB</Emphasis>′O<Subscript>3</Subscript> perovskite-structure solid solutions

A model is considered in which atoms A and A′ or B and B′ of disordered solid solutions A _x A _1?x ^′ BO₃ and AB _x B _1?x ^′ O₃ are distributed over a regular system of points 1(a) and 1(b) of the symmetry group O _h ¹ characterizing the ideal perovskite structure. The probabilities P(G _i |x) of unit cells having crystal-field symmetry at their center lowered to G _i =T _d , D_3d, C_3v, C_4v, D_2h, C_2v, C _s , or C₂ are calculated as a function of the concentration x. The limits for x in which the Jahn-Teller and/or dipole ordering mechanism is probable are determined. In the approximation taking into account only effective pair interactions, the scattering amplitude F _hkl is found to depend on a single parameter r₀. The theory predicts that the dependence of the intensities of even and odd reflections on sin θ/λ is nonmonotonic and that the distributions of nonuniform strains and of values of the lattice parameters in solid solutions are discrete.     

Peculiarities of magnetic field-induced ferromagnetic ordering in narrow-band manganites

The temperature dependences of the residual magnetization in narrow-band manganites (Pr_0.67Ca_0.33MnO₃, Sm_0.55Sr_0.45Mn¹⁸O₃, Sm_0.55Sr_0.45Mn¹⁶O₃, and (NdEu)_0.55Sr_0.45Mn¹⁸O₃) have been studied. All compounds studied are characterized by a fairly high residual magnetization M _R (about 0.5 μ_B/Mn) at 4.2 K, which vanishes upon sample heating to the temperature T _RE ≈ 30–35 K, which is much lower than the temperature T _C of the ferromagnetic transition. However, upon magnetization of the samples at T _RE < T < T _C , the residual magnetization (smaller in magnitude) remains up to T _C . For the composition (NdEu)_0.55Sr_0.45Mn¹⁸O₃, the residual magnetization remains at T < T _C , independent of the temperature of magnetization. The disappearance of the residual magnetization found at intermediate temperatures is apparently related to the destruction of the magnetic field-induced ferromagnetic ordering (which contains an additional contribution of the rare-earth sublattice).     

Synthesis,structure, and optical and photocatalytic properties of quasi-one-dimensional ZnO doped with Со<Subscript>3</Subscript>O<Subscript>4</Subscript> and carbon

One-dimensional nanocomposites Zn_1–x Co _x O_1–y С _у :nCo₃O₄ and solid solutions Zn_1–x Co _x O_1–y С _у , which are promising photocatalysts for the oxidation of toxic organic compounds in visible light, are obtained via the thermolysis of Zn_1–x Co _x (HCOO)(OCH₂CH₂O)_1/2 (0.1 ≤ x ≤ 0.5) precursor in a controlled gaseous atmosphere.     

Mechanism of <Emphasis Type="Italic">F</Emphasis>-center luminescence in anion-defective aluminum oxide single crystals

New experimental data illustrating the effect of deep traps on the luminescence properties of anion-defective α-Al₂O₃ single crystals are presented. It was established that deep traps have electronic nature and their filling occurs through photoionization of F centers and is accompanied by F → F⁺-center conversion. Model concepts were developed that describe the luminescence mechanism in anion-defective aluminum oxide single crystals with inclusion of thermal ionization of the excited F-center states. The validity of the model was supported by experimental data obtained in a study of thermoluminescence, thermally stimulated exoelectron emission, and thermally stimulated electrical conductivity.     

Synthesis and investigation of reentrant oxide superconductors

The conditions for the occurrence of reentrant superconductivity in granular superconductors are studied. The parameters of synthesis of the ceramic samples of CaLaBaCu₃O _x , SrLaBaCu₃O _x and YBa_2–x Sr _x Cu₃O _y Se _z compositions, the results of their microstructure research, the elemental composition and the temperature dependence of the resistance are given. Samples are obtained, which reproducibly exhibit the reentrant superconductivity after the tens of thermal cycling. The relationship between the occurrence of reentrant superconductivity and the oxygen content in the samples was not established.     

Laser Ablation of Metals by Low-Density Picosecond Pulses

Thresholds of laser ablation ofmetals for the picosecond range of laser pulse duration are determined. Within the two-temperature metal model, the space-time dependences of the electron and lattice temperature are obtained. It is shown that ablation parameters become dependent on the pulse duration at the pulse duration τ _p ≥ τ _ie , where τ _ie is the cooling time of the electron gas. For noble metals, such pulse durations are τ _p ≈ 3 ? 10 ps.     

Mechanisms of ionization of <Emphasis Type="Italic">F</Emphasis><Subscript>2</Subscript>-centers in laser media on the basis of LiF crystals

F₂ color centers with a superhigh concentration (5000-cm^–1 absorption coefficient at 450 nm) were formed by high-density electron beams in a layer of LiF crystals of micrometer thickness. The F₂-centers excited by high-power nanosecond wide-band optical pulses (the “soft” pumping regime) efficiently amplified the laser radiation and showed high stability under these conditions. A low stability of F₂-centers to laser radiation (the “hard” excitation regime) is explained by the dissociation of (F ₂ ⁺ , F^–) pairs induced by two-step ionization of F₂-centers: (2hν > 4.5 eV) → F₂ → (F₂)* → F ₂ ⁺ + e; F + e → F^–; F ₂ ⁺ + F^– → 3F.