Investigation on self activated and copper activated zinc sulphide

The diamagnetic susceptibility of zinc sulphide decreases on heat treatment and becomes less temperature dependent. The susceptibilities or the differences in susceptibilities of the pure and activated samples do not obey Curie Law. The susceptibility follows a relation of the typeX _T =X ₀ +X ₁ e ^?E/KT in which bothX ₀ andX ₁ have the same sign.X ₀ is interpreted as true diamagnetic susceptibility of the sample and gradually increases in value with activation,X ₁ depends on the particle size and is found to decrease with the increase in particle size. This is interpreted as being due to surface electrons.“E” as measured in this way is found to be of the order of 0·01 ev. in all cases. Thus“E” seems to be the average surface trap depth of zinc sulphide. It has also been found that in zinc sulphide with low copper concentration the luminescent centres are diamagnetic; copper ions are present presumably in substitutional positions. For zinc sulphide containing high concentration of copper, the presence of paramagnetic centres are detected. It is suggested that in this case copper is present not only at the regular lattice positions acting as luminescent centre but also settles at special lattice sites like dislocation jogs.     

The Hammond postulate: A quantitative interpretation

The Hammond postulate is considered in terms of the model of intersecting parabolas. It is shown that, in radical detachment reactions of the type X _f ^· + HX _i → X _f H + X _i ^· with a symmetrical reaction center X _i …H…X _f , the H atom in the transition state is equidistant from the X _i and X _f atoms if the enthalpy of the reaction ΔH = 0. The X _i …H distance increases and the X _f …H distance decreases linearly as ΔH grows. The dependence remains linear over the range ΔH _min ≤ ΔH ≤ H _max. The same result was obtained in quantum-chemical calculations for reactions of the type R _f ^· + R _i H. In reactions of the type X^· + HY → XH + Y^· with an asymmetric reaction center X…H…Y, the X…H and Y…H interatomic distances in the transition state at ΔH = 0 depend on the force constants and lengths of the X-H and Y-H bonds. The Y…H distance increases and the X…H distance decreases linearly as ΔH grows. A similar picture is observed in the model of intersecting Morse curves, where the dependence of interatomic distances on ΔH in the transition state is nonlinear. Equations describing interatomic distances in the transition state as functions of the enthalpy of the reaction are presented.     

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).     

Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO₄) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B ₀ = 8000 G). The degree of orientation of these complexes is rather high (S _z = 0.76) and close to that of systems with a complete ordering (S _z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH₄, N₂H₄ · H₂O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.     

Structure and Surface Morphology of Cd<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se Epitaxial Films

Cd_1–xMn _x Se (х = 0.03) epitaxial films are produced by the molecular beam condensation method in a vacuum chamber with a residual pressure of 10^–4 Pa on mica and glass substrates. It is established that at room temperature and at a substrate temperature of T = 573 K films of polycrystalline structure grow on the mica substrates, but films of both polycrystalline and amorphous structure grow on the glass substrates. It is shown that the polycrystalline Cd_1–xMn _x Se (х = 0.03) films, unlike the bulk crystals, have a sphalerite-type structure with a lattice parameter of a = 6.05 Å. Increasing the substrate temperature to 673 K leads to epitaxial growth with the direction [111]. Dark aggregates, observed on the film surface, are removed using a source of compensating Se vapors during the growth process. The optimal conditions for the production of structurally perfect epitaxial films are defined.     

Structural transformations of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals with variations in temperature

Single crystals of the K₃H(SO₄)₂ compound are investigated using X-ray diffraction on Xcalibur S and Bruker diffractometers. The structure of the low-temperature monoclinic phase is refined (space group C2/c, z = 4, a = 14.698(1) Å, b = 5.683(1) Å, c = 9.783(1) Å, β = 103.01(1)°, T = 293 K, Bruker diffractometer), the structural phase transition is revealed, and the structure of the high-temperature trigonal phase is determined (space group R \(\bar 3\) m, z = 3, a = 5.73(1) Å,c = 21.51(1) Å,T = 458 K, Xcalibur diffractometer).     

Magnetic and electrical properties of crystalline materials based on indium and copper chalcogenides in a wide range of temperatures and pressures

The effect of temperatures (2–300 K) and high pressures (to 50 GPa) on the electrical and magnetic properties of crystalline materials based on copper and indium chalcogenides with the general formula (InB)_1?x (CuAB ₂)_x, where A = As, Sb; and B = S, Se, and also crystalline CuInSe₂ and CuInS₂, has been studied.     

Lattice IR spectroscopy of Zn<Subscript>1 −<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se epitaxial layers grown on a GaAs substrate by molecular-beam epitaxy

Based on the results from comparison of the data on lattice reflection for Zn_{1 ?x} Cd _x Se bulk crystals (x = 0.08, 0.22) and Zn_{1 ?x} Cd _x Se thin layers of the same compositions grown on GaAs, a more adequate interpretation is given to the lattice IR reflection spectra of Zn_{1 ?x} Cd _x Se alloy films (x = 0–0.55) grown on a GaAs substrate by molecular-beam epitaxy. In this composition region, two ZnSe-and CdSe-like lattice modes are observed corresponding to a double-mode type of rearrangement of the vibration spectrum with varying x. A weak (with oscillator strength smaller than 0.25) high-frequency mode (with respect to the dominant modes) at 220 cm^?1 is also observed.     

A Raman study of lattice vibrations in II–VI semiconductors doped with 3<Emphasis Type="Italic">d</Emphasis> elements

Room-temperature Raman spectra were obtained for powder samples of Zn_1?xNixSe and Zn_1?yCr_ySe compounds and for a single-crystal Zn_1?xNi_xSe (x = 0.0025) sample in the temperature range 5–140 K. The results obtained are interpreted in terms of large-scale lattice shear strains induced by 3d elements in these solid solutions.     

A statistical model of a metallic inclusion in semiconducting media

The atomic dynamics of the binary Al_100–xCu_x system is simulated at a temperature T = 973 K, a pressure p = 1.0 bar, and various copper concentrations x. These conditions (temperature, pressure) make it possible to cover the equilibrium liquid Al_100–xCu_x phase at copper concentrations 0 ≤ x ≤ 40% and the supercooled melt in the concentration range 40% ≤ x ≤ 100%. The calculated spectral densities of the time correlation functions of the longitudinal \({\tilde C_L}\)(k, ω) and transverse \({\tilde C_T}\)(k, ω) currents in the Al_100–xCu_x melt at a temperature T = 973 K reveal propagating collective excitations of longitudinal and transverse polarizations in a wide wavenumber range. It is shown that the maximum sound velocity in the v_L(x) concentration dependence takes place for the equilibrium melt at an atomic copper concentration x = 10 ± 5%, whereas the supercooled Al_100–xCu_x melt saturated with copper atoms (x ≥ 40%) is characterized by the minimum sound velocity. In the case of the supercooled melt, the concentration dependence of the kinematic viscosity ν(x) is found to be interpolated by a linear dependence, and a deviation from the linear dependence is observed in the case of equilibrium melt at x < 40%. An insignificant shoulder in the ν(x) dependence is observed at low copper concentrations (x < 20%), and it is supported by the experimental data. This shoulder is caused by the specific features in the concentration dependence of the density ρ(x).     

Investigations on the local structure and the spin-Hamiltonian parameters for the tetragonal Cu<Superscript>2+</Superscript> centre in ZnGeF<Subscript>6</Subscript>⋅6H<Subscript>2</Subscript>O crystal

The spin-Hamiltonian parameters (g factors g_∥, g_⊥ and hyperfine structure constants A_∥, A_⊥) and the local structure for the tetragonal Cu²⁺ centre in trigonal ZnGeF₆?6H₂O crystal are theoretically studied using the perturbation formulae of these parameters for a 3 d⁹ ion in tetragonally elongated octahedra. In the calculations, the contributions to the spin-Hamiltonian parameters from ligand orbital and spin-orbit coupling are included on the basis of the cluster approach in view of moderate covalency of the studied systems, and the required crystal-field parameters are obtained using the superposition model and the local structures of the studied [Cu(H₂O)₆] ²⁺ cluster. According to the calculations, the ligand octahedra around Cu²⁺ suffer relative elongation τ (≈ 0.085 Å) along the [0 0 1] (or C₄) axis for the tetragonal Cu²⁺ centres in ZnGeF₆?6H₂O crystal, due to the Jahn–Teller effect. The calculated results show good agreement with the experimental data.     

Charge transfer over localized states in a TlS single crystal

It is revealed that TlS single crystals exhibit a variable range hopping conduction along a normal to their natural layers at temperatures T ≤ 230 K in a dc electric field and a nonactivated hopping conduction at low temperatures in strong electric fields. Estimates are made for the density of states near the Fermi level (N _F = 2.8 × 10²⁰ eV^?1 cm^?3 and their energy spread (ΔW = 0.02 eV), the localization radius (a = 33 Å), the average jump distance in the region of activated (R _av(T) = 40 Å) and nonactivated (R _av(F) = 78 Å) hopping conduction, and also the drop in the charge carrier potential energy along the jump distance in an electric field F: eFR = 0.006 and 0.009 eV at F = 7.50 × 10³ and 1.25 × 10⁴ V/cm, respectively.     

Atomic structure of a 1<Emphasis Type="Italic">T</Emphasis>-TiSe<Subscript>2</Subscript> surface layer from photoelectron and Auger electron holography data

A three-dimensional (3D) reconstruction of the atomic structure of the (100) surface of a 1T-TiSe₂ layered dichalcogenide crystal has been performed from X-ray photoelectron and Auger electron diffraction data. The diffraction patterns of the emission of Auger electrons of Se(LMM) selenium and photoelectrons of Ti2p titanium have been considered as holographic diagrams. Being processed with the scattering pattern extraction algorithm using the maximum entropy method (SPEA-MEM), they provide individual 3D images of the nearest environment of selenium and titanium atoms in the TiSe₂ lattice. Using reconstructed 3D images, the positions of 128 atoms in the 2 × 2 × 1.5-nm region of the surface layer of TiSe₂ have been determined. The structure of the surface has a 1T polytype. Interatomic distances in the layer and van der Waals gap are larger than the respective parameters in the bulk of the crystal. It is assumed that titanium layers in two Se-Ti-Se upper surface structural units are displaced along the [001] axis. The structure of the surface layer can be described by a unit cell of the P3 space group with the parameters a = 3.85 Å and c = 14.4 Å.     

X-ray structure analysis of the polycrystalline complex of copper (II) chloride with 1,5-dimethyltetrazole. Application of synchrotron radiation and laboratory diffraction data

The structure of the complex of copper (II) chloride CuCl₂ L, where L is 1,5-dimethyltetrazole, was refined with the Rietveld method using three sets of powder diffraction data obtained at laboratory diffractometers and with synchrotron radiation. The comparative analysis of the results of the structure refinement was performed; this analysis showed that the application of the laboratory data for the wavelength of X-rays λ = 1.7902 Å (CoKα radiation) provides the structural characteristics of the complex comparable in accuracy with those obtained using the synchrotron radiation for the wavelength λ = 1.5443 Å.     

Why <Emphasis Type="Italic">X</Emphasis>(3872) is not a molecule

We discuss the scenario where the X(3872) resonance is the \(c\bar c\) = χ_c1(2P) charmonium which “sits on” the D*⁰\({\bar D^0}\) threshold. We explain the shift of the mass of the X(3872) resonance with respect to the prediction of a potential model for the mass of the χ_c1(2P) charmonium by the contribution of the virtual D*\(\bar D\) + c.c. intermediate states into the self energy of the X(3872) resonance. This allows us to estimate the coupling constant of the X(3872) resonance with the D*⁰\({\bar D^0}\) channel, the branching ratio of the X(3872) → D*⁰\({\bar D^0}\) + c.c. decay, and the branching ratio of the X(3872) decay into all non-D*⁰\({\bar D^0}\) + c.c. states. We predict a significant number of unknown decays of X(3872) via two gluon: X(3872) → gluongluon → hadrons. We suggest a physically clear program of experimental researches for verification of our assumption.     

Random Walk with Barycentric Self-interaction

We study the asymptotic behaviour of a d-dimensional self-interacting random walk (X _n ) _n∈? (?:={1,2,3,…}) which is repelled or attracted by the centre of mass \(G_{n} = n^{-1} \sum_{i=1}^{n} X_{i}\) of its previous trajectory. The walk’s trajectory (X ₁,…,X _n ) models a random polymer chain in either poor or good solvent. In addition to some natural regularity conditions, we assume that the walk has one-step mean drift

$\mathbb{E}[X_{n+1} - X_n \mid X_n - G_n = \mathbf{x}] \approx\rho\|\mathbf{x}\|^{-\beta}\hat{ \mathbf{x}}$

for ρ∈? and β≥0. When β<1 and ρ>0, we show that X _n is transient with a limiting (random) direction and satisfies a super-diffusive law of large numbers: n ^?1/(1+β) X _n converges almost surely to some random vector. When β∈(0,1) there is sub-ballistic rate of escape. When β≥0 and ρ∈? we give almost-sure bounds on the norms ‖X _n ‖, which in the context of the polymer model reveal extended and collapsed phases.

Analysis of the random walk, and in particular of X _n ?G _n , leads to the study of real-valued time-inhomogeneous non-Markov processes (Z _n ) _n∈? on [0,∞) with mean drifts of the form

$ \mathbb{E}[ Z_{n+1} - Z_n \mid Z_n = x ] \approx\rho x^{-\beta} - \frac {x}{n},$

(0.1)

where β≥0 and ρ∈?. The study of such processes is a time-dependent variation on a classical problem of Lamperti; moreover, they arise naturally in the context of the distance of simple random walk on ? ^d from its centre of mass, for which we also give an apparently new result. We give a recurrence classification and asymptotic theory for processes Z _n satisfying (0.1), which enables us to deduce the complete recurrence classification (for any β≥0) of X _n ?G _n for our self-interacting walk.

     

Multicomponent <Emphasis Type="Italic">n</Emphasis>-(Bi,Sb)<Subscript>2</Subscript>(Te,Se,S)<Subscript>3</Subscript> solid solutions with different atomic substitutions in the Bi and Te sublattices

The thermoelectric properties of n-Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions are studied in the temperature range 300–550 K. It is shown that an increase in the parameter β determining the figure-of-merit Z of the material is observed in compositions with the optimally related effective mass of the density of states m/m ₀, the carrier mobility μ₀, and the lattice thermal conductivity κ _L . Within the temperature range 300–350 K, the parameter β and the figure-of-merit Z are found to increase in solid solutions with substitutions in both bismuth telluride sublattices Bi → Sb and Te → Se, S (x = 0.16, y = z = 0.12) for optimum electron concentrations. An increase in the electron concentration and substitutions of atoms only in the tellurium sublattice bring about an increase in the β parameter and the value of Z at higher temperatures. Within the range 350–450 K, the parameters β and Z are observed to increase in a solid solution with a low content of substituted atoms in the tellurium sublattice Te → Se, S for y = z = 0.09 and, at higher temperatures up to 550 K, in compositions with tellurium substituted by selenium only, with increasing content of substituted atoms.     

Anion height dependence of <Emphasis Type="Italic">T</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript> and the density of states in iron-based superconductors

Systematic ab initio LDA calculations were performed for all the typical representatives of recently discovered class of iron-based high-temperature superconductors: REOFe(As,P) (RE = La, Ce, Nd, Sm, Tb), Ba₂Fe₂As, (Sr,Ca)FFeAs, Sr₄Sc₂O₆Fe₂P₂, LiFeAs and Fe(Se,Te). Non-monotonic behavior of total density of states at the Fermi level is observed as a function of anion height relative to Fe layer with maximum at about Δz _a ～ 1.37 Å, attributed to changing Fe-As (P, Se, Te) hybridization. This leads to a similar dependence of superconducting transition temperature T _c as observed in the experiments. The fit of this dependence to elementary BCS theory produces semiquantitative agreement with experimental data for T _c for the whole class of iron-based superconductors. The similar fit to Allen-Dynes formula underestimates T _c in the vicinity of the maximum, signifying the possible importance of non-phonon pairing in this region. These results unambiguously demonstrate that the main effect of T _c variation between different types of iron-based superconductors is due to the corresponding variation of the density of states at the Fermi level.     

Scattering the Geometry of Weighted Graphs

Given two weighted graphs (X, b_k, m_k), k =?1,2 with b₁ ～ b₂ and m₁ ～ m₂, we prove a weighted L¹-criterion for the existence and completeness of the wave operators W_±(H₂, H₁, I_1,2), where H_k denotes the natural Laplacian in ?²(X, m_k) w.r.t. (X, b_k, m_k) and I_1,2 the trivial identification of ?²(X, m₁) with ?²(X, m₂). In particular, this entails a general criterion for the absolutely continuous spectra of H₁ and H₂ to be equal.     

Extended <Emphasis Type="Italic">E</Emphasis>(5) and <Emphasis Type="Italic">X</Emphasis>(5) symmetries: Series of models providing parameter-independent predictions

The E(5) symmetry describes nuclei related to the U(5)-SO(6) phase transition, while the X(5) symmetry is related to the U(5)-SU(3) phase transition. First, a chain of potentials interpolating between the U(5) symmetry of the five-dimensional harmonic oscillator and the E(5) symmetry is considered. Parameter-independent predictions for the spectra and B(E2) values of nuclei with R₄ = E(4)/E(2) ratios of 2.093, 2.135, and 2.157 (compared to the ratio of 2.000 of the U(5) case and the ratio of 2.199 of the E(5) case) are derived numerically and compared to existing experimental data, suggesting several new experiments. TheX(5) symmetry describes nuclei characterized byR₄=2.904.Using the same separation of variables of the original Bohr Hamiltonian as in X(5), an exactly soluble model with R₄=2.646 is constructed and its parameter-independent predictions are compared to existing spectra and B(E2) values. In addition, a chain of potentials interpolating between this new model and the X(5) symmetry is considered. Parameter-independent predictions for the spectra and B(E2) values of nuclei with R₄ ratios of 2.769, 2.824, and 2.852 are derived numerically and compared to existing experimental data, suggesting several new experiments.