Evolution of a Non-Uniform Deformed State in the Structure of Zinc-Chalcogenide Cubic Crystals Doped by 3 d Ions

The real structure of bulk Zn1 – хМхSe (S) crystals of diluted magnetic semiconductors with М = V, Cr, Fe, Co, Ni 3d impurities is characterized by neutron diffraction. These impurities are known to greatly destabilize even the initial lattices of pure zinc chalcogenides. Data on the resulting non-uniform microstrain field induced by atomic displacements are obtained from the structural peaks along the tangential and radial directions on the above crystals within a dopant concentration range of 0.01 ≤ х ≤ 0.10. Additional nodes with q = (1/3 1/3 1/3) 2π/a (q is the wave vector and a is the cubic unit cell) emerging in the reciprocal lattice of the cubic structure are considered as evidence for a pre-transition to the fcc (face-centered cubic)–hcp (hexagonal close-packed) phase state, which implies transitions from the fcc lattice along an 8-ray non-Lifshitz star with the wave vector k5 = μ(b1 + b2 + b3), where b1, b2, b3 are the reciprocal lattice vectors and μ ≈ 1/3.     

Nuclear superstructure {1/2, 0, 1/2} of an La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> manganite orthorhombic crystal

The {1/2, 0, 1/2} nuclear superstructure in an La_0.93Sr_0.07MnO₃ manganite orthorhombic crystal is revealed using thermal-neutron diffraction. It is demonstrated that this superlattice belongs to the class of distortion-type structures and is directly associated with a 1/16-type ordering of Mn⁴⁺ and Mn³⁺ ions in a collinear ferromagnetic phase of the La_0.93Sr_0.07MnO₃ manganite.     

Magnetic structure and transport properties of atomically disordered crystals of two-dimensional manganites La2−2x Sr1+2x Mn2O7

The magnetic structure and transport properties of partially disordered crystals of two-dimensional manganites La_2?2x Sr_1+2x Mn₂O₇ (x = 0.3, 0.4) are studied over a wide range of temperatures. The crystals are transformed into an atomically disordered state under irradiation with fast neutrons at a dose of 2 × 10¹⁹ cm^?2. The average concentration of substitutional defects in the crystal is ≈4%. It is found that substitutional defects are responsible for the transition of these manganites from the ferromagnetic metal state to the insulator state with a spin glass structure. The results obtained are discussed in terms of the ratio between the kinetic energy of charge carriers and the exchange energy of localized spins.     

Poisson-Lie T-duality and complex geometry in N = 2 superconformal WZNW models

Poisson-Lie T-duality in N = 2 superconformal WZNW models on the real Lie groups is considered. It is shown that Poisson-Lie T-duality is governed by the complexifications of the corresponding real groups endowed with Semenov-Tian-Shansky symplectic forms, i.e. Heisenberg doubles. Complex Heisenberg doubles are used to define on the group manifolds of the N = 2 superconformal WZNW models the natural actions of the isotropic complex subgroups forming the doubles. It is proved that with respect to these actions N = 2 superconformal WZNW models admit Poisson-Lie symmetries. The Poisson-Lie T-duality transformation maps each model onto itself but acts non-trivially on the space of classical solutions.     

Quantum chemical analysis of the Eley-Rideal and Langmuir-Hinshelwood mechanisms of the catalytic oxidation of carbon monoxide on the nickel surface

The studies concerned with the oxidation of carbon monoxide on the nickel surface are reviewed. The Eley-Rideal (ER) collision and Langmuir-Hinshelwood (LH) adsorption mechanisms of the oxidation are analyzed. Calculations of the activation barriers of the oxidation of carbon monoxide on the Ni (111), (100), and (110) faces were performed for the first time and involved optimization of the reaction paths by the collision and adsorption mechanisms. It is shown that on the Ni (111) and (110) faces the ER collision mechanism of the reaction is preferable with the activation barriers ΔE _dis ^O ₂=62 kJ/mole and ΔE _trans ^O A21F5001₂x=25 kJ/mole for Ni (111) and ΔE _dis ^O ₂=72 kJ/mole and ΔE _trans ^O ₂=20 kJ/mole for Ni (110); on the Ni (100) face, the LH adsorption mechanism with the activation barriers ΔE _dis ^O ₂=75 kJ/mole and ΔE _trans ^O ₂=42 kJ/mole is favored. Analysis of the potential barriers for the catalytic oxidation of carbon monoxide on the Ni surfaces suggests the LH mechanism to be preferential, although insignificant differences in the activation barries can lead to the oscillatory reaction mechanism, which is confirmed experimentally. The calculations were performed by the LCAO MO SCF method in the MINDO/3 approximation. Kiev Polytechnical Institute. Translated fromZhurnal Struktumoi Khimii, Vol. 37, No. 4, pp. 628–645, July–August, 1996. Translated by I. Izvekova     

Enhanced spin capturing polymerization: Numerical investigation of mechanism

Simulation on the kinetic scheme of enhanced spin capturing polymerizations (ESCP) were performed to reveal the influence of different parameters, e.g., initiation rate, spin capturing and side reactions on the properties (the monomer conversion, degree of polymerization, polydispersity index, and the fraction of “living” chains) of polymer obtained. The kinetic scheme of ESCP was solved numerically as well as the method of statistical moments of molecular weight distribution was applied to get some numerical expressions for analysis. The simulations showed that fast initiation rate can lead to decrease of living fraction and broadening of molecular weight distribution. Whereas high rate of spin capturing makes the polymer chains shorter but increases living character. And side reactions always decrease livingness of the polymer obtained. Finally in the case of absence of side reaction we were able to formulate criteria for formation of polymer with target molecular weight and quota of living chains via ESCP process. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2546–2556     

Ferromagnetically Coupled S=1 Chains in Crystals of Verdazyl-Nitronyl Nitroxide Diradicals

Thermally stable organic diradicals with a triplet ground state along with large singlet-triplet energy gap have significant potential for advanced technological applications. A series of phenylene-bridged diradicals with oxoverdazyl and nitronyl nitroxide units were synthesized via a palladium-catalyzed cross-coupling reaction of iodoverdazyls with a nitronyl nitroxide-2-ide gold(I) complex with high yields. The diradicals exhibit high stability and do not decompose in an inert atmosphere up to 180 °C. For the diradicals, both substantial AF (ΔE_ST≈−64 cm⁻¹) and FM (ΔE_ST≥25 and 100 cm⁻¹) intramolecular exchange interactions were observed. The sign of the exchange interaction is determined both by the bridging moiety (para- or meta-phenylene) and by the type of oxoverdazyl block (C-linked or N-linked). Upon crystallization, diradicals with the triplet ground state form unique one-dimensional exchange-coupled chains with strong intra- and weak inter-diradical ferromagnetic coupling.     

Short-wavelength atomic-displacement modulation preceding the <Emphasis Type="Italic">B</Emphasis>2 → <Emphasis Type="Italic">B</Emphasis>19′ martensitic transformation in a TiNi-based alloy

Neutron diffraction studies of the fine structure of a Ti₄₉Ni₅₁ single crystal are performed before the onset of the B2 → B19′ martensitic transformation (temperature of the onset of the transformation M _s =200 K). Upon cooling below 460 K, extra reflections are found to form; their positions in the B2-phase reciprocal lattice correspond to the full non-Lifshitz star of the wave vector q=0.225〈112〉. At temperatures below 430 K, 0.45〈110〉 extra reflections appear, corresponding to second-order diffraction effects. In the temperature range 300–460 K, reversible and nonhysteretic changes in the intensities and positions of both types of extra reflections are observed. Analysis of the intensities and spatial distribution of the extra reflections in the B2-phase reciprocal lattice indicates that a displacive superstructure dominated by longitudinally polarized atomic-displacement waves with q=0.225〈112〉 arises in the single crystal in the pretransition temperature range.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.