Fluorides of ruthenium and chromium: Theoretical studies

The electronic and structural characteristics of CrF₅, CrF₄, RuF₅ and RuF₄ were studied. Ab initio (SCF-CI) calculations were performed with different structures and spin states for each complex. The favored conformation always corresponds to the highest multiplicity: doublet for CrF₅ in D_3h, triplet for CrF₄ in T_d, quadruplet for RuF₅ in C_4v and quintuplet for RuF₄ in D_4h symmetry.     

Formation of Diol Divinyl Diethers in the Synthesis of 1,2-Epoxy-3-(vinyloxyalkoxy)propanes

Russian Journal of Organic Chemistry -     

Effect of high pressures on the mechanical and electrical properties of barium chalcogenides

In this work, on the basis of a semiempirical model of bonding forces that allows for three-particle interaction and uses the pseudopotential method, the mechanical and electrical properties of barium chalcogenides are studied at hydrostatic pressure. Equations of state are formulated from hydrostatic compression, parameters of the type B1–B2 structural phase transitions are calculated, the change in the energy band spectrum under the influence of the pressures is studied, and an estimate is made of the critical amount of compression that induces a dielectric-metal phase transition. The results obtained are in agreement with the available data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 44–52, November, 1991.     

Fibre stability in anisotropic matrix at small strains

As acknowledged in almost all monographs on the fracture of composite materials, one of the major fracture mechanism in unidirectional fibrous composites under uniaxial compression along the reinforcing elements is the stability loss of the material structure (the structural instability). According to this mechanism, theoretical investigations of the fracture along the fibres are reduced to those of the stability loss in the material structure, and the value of external critical forces is accepted as the value of failure forces. At present, numerous theoretical investigations have been carried out in this field with the use of the three-dimensional linearized theory of stability in the framework of the piecewise-homogeneous body model. However, in all the investigations it is assumed that the matrix and the fibre material are isotropic. It is evident that in many cases it is necessary to take into account the anisotropy of the matrix material when investigating the stability loss of fibres. In view of the above, in the framework of the piecewise-homogeneous body model using the three-dimensional linearized theory of stability, the present paper considers the stability loss of the fibre in the anisotropic (transversally isotropic) matrix. The effect of the properties of the matrix material on the critical values of the external loading is examined.Submitted to the 10th International Conference of Mechanics of Composite Materials (Riga, April 20–23, 1998).Published in Mekhanika Kompozitnykh Materialov, Vol. 33, No. 5, pp. 603–611. September–October, 1997.     

Mechanisms of ion-beam-enhanced diffusion in amorphous silicon

We have investigated ion-beam-enhanced diffusion of Au in undoped and B doped amorphous Si. The diffusion coefficients depend linearly on ion flux and exibit an Arrhenius-like temperature dependence with an activation energy of 0.37 eV in the temperature range 200–350° C. Moreover the diffusivity is enhanced by a factor of 5 by B-doping at a concentration of 1×10²⁰ atoms/cm³. A similar enhancement is observed in thermal diffusion of Au which has an activation energy of 1.5 eV. On the basis of these results a model for the ion-beam-enhanced diffusion of Au is proposed where the high density of defects present in amorphous Si act as traps for the fast moving interstitial Au atoms. The effectiveness of this trapping process can be changed by the high concentration of mobile defects generated by the beam and also by a change in the charge state of the traps induced by the presence of B.     

New fir laser lines and frequency measurements from optically pumped13CD3OH3

We report the discovery of 57 new fir laser lines from¹³CD₃OH molecule optically pumped by a waveguide CO₂ laser of 300 MHz tunability. For all lines, precise frequency offset measurements between the CO₂ line center and the center of the absorbing¹³CD₃OH line were performed using the transferred Lamb-Dip technique. We have also measured directly the frequency of seven FIR laser lines by heterodyning with already known laser lines. We present a complete list of all known laser lines (134) and frequency measurements (24) for this molecule.Work supported by CNPq, FAPESP, FAEP-Brasil, and CNR-Italia     

The structure of the nematic-isotropic interface in polymer systems

The structure of the nematic-isotropic interfacial layer is studied theoretically for systems formed by rod-like and persistent macromolecules. It is shown that the width of interfacial layer is normally of the order of the straight part of a molecule. This allows us to use the approach which describes intermolecular interactions phenomenologically (i.e. it allows us to consider all interactions), at the same time this approach describes molecular flexibility microscopically (i.e. it allows us to study the effects of flexibility correctly). It was found, that non-monotonic gradient profiles in the surface layer of the order parameter or of the concentration of molecules as a function of the coordinate perpendicular to the interface are possible. For example, a thin layer with abnormal ordering of molecules along the surface may exist near the interface for some systems.     

Kinetics and mechanism of oxidation of indigo carmine by hypohalites

Kinetics of oxidation of indigo carmine (IC) by sodium hypohalites, NaOX (X ? Cl or Br), in alkaline buffer of pH 9–11 has been studied spectrophotometrically at λ = 610 nm. The experimental rate law obtained is ?d[IC]/dt = k[OX^?][IC][OH^?]^x where x <1. Variation of ionic strength or dielectric constant of the medium had no effect on the reaction rate while the addition of halide ions slightly retarded the rate. A most plausible mechanism proposed on the basis of experimental results involves the formation of isatin sulphonate which undergoes further oxidation to anthranilate. Activation parameters have been evaluated.