Magnetic phases in Mn<Subscript>1</Subscript>_<Subscript>x</Subscript>Fe<Subscript>x</Subscript>WO<Subscript>4</Subscript> studied by neutron powder diffraction

The magnetic structures of Mn_1-xFe_xWO₄ with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn²⁺- and Fe²⁺-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO₄ and FeWO₄. Received 9 October 2002 Published online 14 March 2003     

Second harmonic generation in In2O3–SiON films doped by Al and Sn

Photoinduced optical and second-order non-linear optical effects in the interfaces separating In₂O₃–SiON (O/N ratio equals 1) films doped with A1, Sn and glass substrates were investigated using the photoinduced optical second harmonic generation. The photoinduced effective second-order optical susceptibility d_eff (at λ=1.76 μm) shows a good correlation with the linear optical susceptibility, particularly with the shift of the absorption edge. The maximal response of the photoinduced optical response signal was observed for the pump–probe delaying time of 34 ps. The performed experimental measurements indicate that the observed effects are mainly caused by the interface potential gradients on the border glass–In₂O₃–SiON film and by additional polarization due to insertion of the Al and Sn atoms. The observed phenomenon may be proposed as a sensitive tool for investigation of thin semiconducting interfacial layers and simultaneously such films may be used as materials for non-linear optical devices.     

Synthesis of β-phenyl-δ,ε-unsaturated amino acids and stereoselective introduction of side chain groups into [4,3,0]-bicyclic β-turn dipeptides

(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings.     

Identification of new catalysts for the asymmetric reduction of imines into chiral amines with polymethylhydrosiloxane using high-throughput screening

The use of high-throughput techniques allowed the rapid identification of new catalysts for the enantioselective reduction of imines using polymethylhydrosiloxane (PMHS) as a reducing agent. By a simple modification of the chiral ligand structure that came out of the screening, the enantioselectivity of the reduction was increased from 40% ee to 60% ee.     

The spline collocation method for parabolic boundary integral equations on smooth curves

Summary. We consider the spline collocation method for a class of parabolic pseudodifferential operators. We show optimal order convergence results in a large scale of anisotropic Sobolev spaces. The results cover the classical boundary integral equations for the heat equation in the general case where the spatial domain has a smooth boundary in the plane. Our proof is based on a localization technique for which we use our recent results proved for parabolic pseudodifferential operators. For the localization we need also some special spline approximation results in anisotropic Sobolev spaces. Received May 17, 2001 / Revised version received February 19, 2002 / Published online April 17, 2002     

Arithmetic expressions of Selberg's zeta functions for congruence subgroups

In [P. Sarnak, Class numbers of indefinite binary quadratic forms, J. Number Theory 15 (1982) 229-247], it was proved that the Selberg zeta function for SL₂(Z) is expressed in terms of the fundamental units and the class numbers of the primitive indefinite binary quadratic forms. The aim of this paper is to obtain similar arithmetic expressions of the logarithmic derivatives of the Selberg zeta functions for congruence subgroups of SL₂(Z). As applications, we study the Brun-Titchmarsh type prime geodesic theorem and the asymptotic formula of the sum of the class number.     

Ionic conductivity of epitactic MBE-grown BaF2 films

We studied parallel conductivities of pure BaF₂ films with thicknesses ranging from 35 to 300 nm, epitaxially grown on Al₂O₃(0 1 2) substrates by molecular beam epitaxy technique. The overall conductivities of the films are found to increase with decreasing thickness. The detailed investigation of the overall conductance as a function of the thickness permits the deconvolution of bulk and boundary effects, the latter being attributed to distinct space charge effects in the interface between BaF₂ film and Al₂O₃ substrate. The (extrinsic) Debye length (λ) is estimated to be about 8 nm at T=593 K, which corresponds to an impurity content of 10¹⁸/cm³ (singly ionized dopant assumed). This is consistent with the fact that we observed a constant boundary contribution for all investigated films (film thickness >4λ). It is also consistent with the Debye length observed in a previous report on CaF₂/BaF₂ heterolayers fabricated by the same technique, in which the low temperature enhancement was also attributed to space charges in BaF₂ [Nature 408 (2000) 946]. Only at low temperatures (below 370 °C), the conductance seems to be influenced by strain effect.     

Organic synthesis based on cathodic deprotonation of acids

The results of studies on electrosynthesis involving carb- and heteroanions generated by cathodic deprotonation of acids (CDA), carried out in the laboratory headed by the author, are surveyed. These studies resulted in the elaboration of efficient electrochemical versions of the known Michaelis-Becker, Wittig-Horner, and Perkin reactions; electrochemical analogs of homolytic aromatic substitution, alkylation, heterocyclization,etc. were developed. Based on CDA, convenient and promising methods for preparing variousN-, O-, P-, S-, andC-alkylated and arylated substances have been developed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1411–1422, August, 1995.The author is grateful to Professor V. A. Dorokhov, Professor V. P. Litvinov, and researchers from the laboratories of N. D. Zelinsky Institute of Organic Chemistry headed by them, who participated in joint studies.The work was carried out with financial support from the International Science Foundation (Grant No. MHYOO).     

Photoemission study of the modification of the electronic structure of transition-metal overlayers on TiO2 surfaces II. Cr on TiO2(0 0 1)

The electronic states of the Cr overlayers on TiO₂(0 0 1) surfaces have been investigated using angle-resolved and resonant photoemission spectroscopy with synchrotron radiation. At lower coverages, Cr deposition on TiO₂(0 0 1) creates two well separated in-gap emissions due to the formation of surface Ti³⁺ (3d¹) ions and Cr³⁺ (3d³) ions. At higher coverages, the in-gap emission is developed into the 2-peak-structure emission of Cr 3d character. The corresponding state is considered to be of metallic nature from the viewpoint of the high ability of oxygen adsorption, but has no Fermi edge, indicating a possibility of forming small Cr clusters on TiO₂(0 0 1) at this stage.