Chlorokomplexe von Cu2+ und Ni2+ in Dimethylformamid

Zusammenfassung Durch spektrophotometrische Messungen in Dimethylformamid (DMF) werden die Koordinationsformen [CuCl]⁺ und [CuCl₃]^– sowie [NiCl]⁺, [NiCl₃]^– und [NiCl₄]^2– nachgewiesen. Bei Nickel(II)-chlorid und Kupfer(II)-chlorid wird Autokomplexbildung diskutiert. Die Solvate [Cu(DMF)₄] (ClO₄)₂ und [Ni(DMF)₆] (ClO₄)₂ werden isoliert.Im Zuge der Untersuchungen über Chlorokomplexe von Ionen der Übergangsmetalle^{1, 2} in nichtwäßrigen Lösungsmitteln wurden die Spektren der Lösungen von Kupfer(II)- und Nikkel(II)-perchlorat inDMF in Gegenwart verschiedener Mengen Tetraäthylammoniumchlorid aufgenommen.Mit 5 Abbildungen     

Yttrium aluminate crystals for slabs

The methods of growing YAG:Nd crystals with a flat interface and YAP:Nd crystals with a sharp conical interface are described. The form of the interface was controlled by the He and H₂O content in the reducing atmosphere composed mainly of Ar and H₂ as well as by axial temperature gradient above the melt level. The crystals of 120–180 mm in length were machined to the high-quality slabs.     

Nd3+ near UV and visible fluorescence in YAP:Nd

The present paper summarizes detailed investigations of Nd³⁺ fluorescence spectra in YAP:Nd laser crystal in the broad spectral range of 370–1100 nm at liquid nitrogen temperature. Especially, Nd³⁺ near UV and visible fluorescence spectra were studied for the first time in this crystal. The Nd³⁺ near UV and visible fluorescence spectra of this crystal consist of many narrow lines (up to 50). The Nd³⁺ near UV and visible fluorescence lines arise mainly from⁴D_3/2 and²P_3/2 Nd³⁺ terms (transitions from⁴D_3/2,²P_3/2 to lower lying Nd³⁺ levels are responsible for their appearance). At room temperature the fluorescence spectra consist of broad bands with narrow lines (mainly⁴D_3/2⁴F_3/2,⁴F_5/2 and²H_9/2 transitions).     

Non-steady state homogeneous nucleation in glass-forming systems: Dimensionless kinetic equation

The kinetic equation of the classical homogeneous nucleation theory is rewritten in dimensionless form and it is shown that the numerical computation of the dimensionless kinetic equation is approximately 20 times faster in comparison with the original kinetic equation. The results are compared with known analytical results and with previous numerical results in the case of the constant and variable temperature for the model Li₂O.2 SiO₂ melt. It is shown, e.g., that under non-isothermal conditions the nucleation rate is greater than the quasistationary nucleation rate and the cluster distribution function is greater than the corresponding quasiequilibrium cluster distribution function.     

XPS investigation of LPE garnet films

XPS spectra of YIG, YIG:Bi, YIG:Ca and YIG:Co(Ge, Ca) epitaxial garnet films were measured at room temperature. The positions of the main iron, yttrium, oxygen, bismuth, cobalt and lead spectral lines were determined and their changes with the surface treatments were investigated. It was found that divalent and trivalent states of iron and cobalt ions can be resolved, the chemical shifts being in oposite directions.The authors would like to thank Dr. J. imová for careful EPMA analysis of the samples.     

Crystal structure and vibrational spectra of hydrazinium (2+) tri-μ-fluoro bis[pentafluorozirconate (IV)] fluoride and vibrational spectra of its hafnium analogue

Monoclinic (N₂H₆)₃Zr₂F₁₃·F crystallizes in space group P2₁-C ₂ ² (No. 4) with unit cell dimensionsa=5.670(1),b=10.984(2),c=10.601(2) Å,=93.88(1)°,V=658.7(4) ų andZ=2. Two different types of N₂H₆ ²⁺ ions are present. One is involved in strong H-bonds to F^– ions in infinite chains running along the a axis (the shortest N-F distance is 2.437(5) Å), and the other links the structure through weaker bi- and trifurcated H-bonds to fluorine ligands of the Zr₂F₁₃ ^5– ions. The N-N bond lengths range from 1.430(5) to 1.446(5) Å with apparently no meaningful correlation to the type of N₂H₂ ²⁺ ions. The Zr₂F₁₃ ^5– ions have very nearly C₂ point symmetry and are formed by joining two distorted bicapped trigonal prisms of ZrF₈-units through a common face. Distances of Zr-F terminal bonds range from 2.015(2) to 2.112(2) Å and of bridging bonds from 2.133(2) to 2.212(2) Å. (N₂H₆)₃Hf₂F₁₃·F is isomorphous. The vibrational spectra of the two compounds are nearly identical, with the exception of a strong infrared band, which is assigned to a stretching mode with the moving central atom within the anion. The anion part of the spectrum is simple, showing broad unresolved bands. The cation part shows two types of N₂H₆ ^– ions. H-Bonding is strongly present in the spectra, but no simple correlations with the H-bond strength is evident.     

Some Landau's type inequalities for infinitesimal generators

Summary Lett T(t) be a strongly continuous contraction semigroup on a complex Banach space and letA be its infinitesimal generator. We prove that, forx D(A ³), the following inequalities hold true: Ax³ 243/8 x²A ³ x, A ² x 24 xA ³ x². Ift T(t) is a contraction group (resp. cosine function) we get the analogous but better inequalities with constants 9/8 and 3 (resp. 81/40 and 72/25) instead of 243/8 and 24. We consider also uniformly bounded semigroups, groups and cosine functions.     

Numerical solution of a singularly perturbed problem via exponential splines

It is proved that a spline difference scheme for a singularly perturbed self-adjoint problem, derived by using exponential cubic splines at mid-points, has second order uniform convergence in a small parameter . Numerical experiments are presented to confirm the theoretical predictions.     

Interlayer pairing in high temperature superconductors: effect of nonmagnetic impurities

The influence of impurity scattering is studied theoretically in a two-layer model for the high-T _c superconductor Y₁Ba₂Cu₃O_7– with intra- and inter-layer pairing. Two types of impurities are considered: (I) impurities which conserve the reflection symmetry of the two layers and (II) impurities which break it. Impurities of type (I) have no influence on the critical temperature. Type (II) impurities have strong influence onT _c as well as onH _c2 if there is a pairing interaction between carriers of different layers. The treatment of type (II) impurities is generalized to a periodic layer model appropriate for La_2–x Ba _x CuO₄. Available experiments on impurities in Y₁Ba₂Cu₃O_7– and La_2–x Ba _x CuO₄ are interpreted with our theory.