Luminescent properties of three structures built from 3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olate and cadmium

Yellow–orange tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN³)cadmium(II) dihydrate, [Cd(C₈HN₄O₂)₂(H₂O)₄]·2H₂O, (I), and yellow tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN³)cadmium(II) 1,4‐dioxane solvate, [Cd(C₈HN₄O₂)₂(H₂O)₄]·C₄H₈O₂, (II), contain centrosymmetric mononuclear Cd²⁺ coordination complex molecules in different conformations. Dark‐red poly[[decaaquabis(μ₂‐3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κ²N:N′)bis(μ₂‐3‐cyano‐4‐dicyanomethylene‐1H‐pyrrole‐2,5‐diolato‐κ²N:N′)tricadmium] hemihydrate], [Cd₃(C₈HN₄O₂)₂(C₈N₄O₂)₂(H₂O)₁₀]·0.5H₂O, (III), has a polymeric two‐dimensional structure, the building block of which includes two cadmium cations (one of them located on an inversion centre), and both singly and doubly charged anions. The cathodoluminescence spectra of the crystals are different and cover the wavelength range from UV to red, with emission peaks at 377 and 620 nm for (III), and at 583 and 580 nm for (I) and (II), respectively.     

Dimensional Hume-Rothery factor and shear stability of bcc solid solutions

The relation between the elastic shear constants and the dimensional Hume-Rothery factor is traced on the basis of the pseudopotential method for a number of bcc solid solutions AB. It is clarified that in the case of a substantial difference between the atomic volumes _A and _B, the constant c=(c₁₁-c₁₂)/2 takes on anomalously low values and even vanishes. The conclusion is hence made that the explanation of the 15% Hume-Rothery rule is possible from the aspect of stability of the crystalline lattice to shear. The presence of lattice distortion is not needed here in principle, as had been assumed earlier. It is shown that ordering of atoms according to the CsCl type can result in an abrupt increase in the value of c, i.e., in stabilizing the lattice of the initial disordered solid solution.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 97–102, March, 1980.     

Metallocene systems in propylene polymerization: Effect of triisobutylaluminum and lewis bases on the behavior of catalysts and properties of polymers

For two stereospecific metallocene catalysts, namely, syndiospecific Ph₂CCpFluHfMe₂ and isospecific rac-Me₂SiInd₂ZrMe₂, the introduction of Lewis bases into a reaction medium was shown to promote a marked rise in the efficiency of catalytic systems. In the case of the syndiospecific metallocene, the maximum effect of the base (a 10-fold increase in activity) was achieved using the (Ph₂CCpFluHfMe₂ + Ph₃N)/CPh₃B(C₆F₅)₄ catalytic system in the presence of Al-i-Bu₃ at a molar ratio of Al: Hf: B: N = 15: 1: 1: 1. When the polymerization of propylene was carried out in the presence of Al-i-Bu₃ and Ph₃N, an elastomeric stereoblock syndio/atactic polypropylene was produced. For the (rac-Me₂SiInd₂ZrMe₂ + amine)/CPh₃B(C₆F₅)₄ catalytic system, a 15-to 30-fold increase in activity was observed upon introduction of amines of the aniline type: Me₂NPh, Me-n-BuNPh, and NPh₃.     

Semiempirical calculations of the electronic spectra of organometallic compounds: Estimation of solvent and counterion effects

The electronic spectra of the [Ru(NH₃)₅pz]²⁺, [Ru(NH₃)₅pz]³⁺, and [Ru(CN)₅pz]³⁻ complexes are calculated by the CI INDO method. The effect of solvation on the spectra is considered in a point charge approximation and in terms of the parametric model of a charged sphere enveloping the metal fragment. Interrelation of these approaches is discussed. Data on the molecular electrostatic potentials created by the complexes are presented to substantiate the models. St. Petersburg State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 4, pp. 603–618, July–August, 1996. Translated by I. Izvekova     

Semiempirical calculations of the electronically excited states of organometallic compounds: Selection of configuration interaction basis sets

Semiempirical INDO-E/S+RCIP calculations of the electronic structures of the ground and excited states of the pyrazine (pz) molecule and [Ru(NH₃)₅pz]^q (q=+1, +2, +3) complexes were performed to analyze the dependence of the calculation results on the active MO space and configuration basis set. Recommendations for the construction of the {Ф_k} basis sets and formation of the {ϕ_k} sets are given. St. Petersburg State University. Translated fromZhurnal Struktumoi Khimii, Vol. 37, No. 2, pp. 206–219, March–April, 1996. Translated by I. Izvekova     

Integration of impurities with large-angle grain boundaries in d-transition metals

The approximation of the liquid model of grain boundaries is used to calculate the bonding energy F of carbon and oxygen interstitial impurities with largeangle grain boundaries in d-transition metals and impurities of d-transition metals in group VIA elements: chromium, molybdenum, and tungsten. It is shown that in the case of interstitial impurities as well as substitutional impurities in d-transition metals the bonding energy is determined by the characteristics of the d-band occupation.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 70–75, April, 1979.     

Fundamental role of crystal structure curvature in plasticity and strength of solids

In the paper, we use the nonlinear multiscale approach of physical mesomechanics to demonstrate that the scales of local crystal structure curvature in solids play a fundamental role in the generation of strain-induced defects and cracks. It is shown that strain-induced defects arise at the interfaces of 2D planar and 3D crystal subsystems by the mechanism of “laser pumping” and cracks nucleate as structural phase decay in the zones of crystal structure curvature where the nonequilibrium thermodynamic potential or so-called Gibbs energy is higher than zero. Nonlinear fracture mechanics eliminates the problem of singularity 1/r in equations of crack growth but requires accounting for local lattice curvature at the crack tip.     

Efficient cardiac diffusion tensor MRI by three-dimensional reconstruction of solenoidal tensor fields

Tensor tomography is being investigated as a technique for reconstruction of in vivo diffusion tensor fields that can potentially be used to reduce the number of magnetic resonance imaging (MRI) measurements. Specifically, assessments are being made of the reconstruction of cardiac diffusion tensor fields from 3D Radon planar projections using a filtered backprojection algorithm in order to specify the helical fiber structure of myocardial tissue. Helmholtz type decomposition is proposed for 3D second order tensor fields. Using this decomposition a Fourier projection theorem is formulated in terms of the solenoidal and irrotational components of the tensor field. From the Fourier projection theorem, two sets of Radon directional measurements, one that reconstructs the solenoidal component and one that reconstructs the irrotational component of the tensor field, are prescribed. Based on these observations filtered backprojection reconstruction formulae are given for the reconstruction of a 3D second order tensor field and its solenoidal and irrotational components from Radon projection measurements. Computer simulations demonstrate the validity of the mathematical formulations and demonstrate that a realistic model of the helical fiber structure of the myocardial tissue specifies a diffusion tensor field for which the first principal vector (the vector associated with the maximum eigenvalue) of the solenoidal component accurately approximates the first principal vector of the diffusion tensor. A priori knowledge of this allows the orientation of the myocardial fiber structure to be specified utilizing one half of the number of MRI measurements of a normal diffusion tensor field study.