Neutron diffraction study of the magnetic ordering in the series R 2 BaNiO 5 (R = Rare Earth)

A neutron diffraction study, as a function of temperature, of the title compounds is presented. The whole family (space group Immm, a ≈ 3.8?, b ≈ 5.8?, c ≈ 11.3?) is structurally characterised by the presence of flattened NiO₆ octahedra that form chains along the a-axis, giving rise to a strong Ni-O-Ni antiferromagnetic interaction. Whereas for Y-compound only strong 1D correlations exist above 1.5 K, presenting the Haldane gap characteristic of 1D AF chain with integer spin, 3D AF ordering is established simultaneously for both R and Ni sublattices at temperatures depending on the rare earth size and magnetic moment. The magnetic structures of R₂BaNiO₅ ( R = Nd, Tb, Dy, Ho, Er and Tm) have been determined and refined as a function of temperature. The whole family orders with a magnetic structure characterised by the temperature-independent propagation vector = (1/2, 0, 1/2). At 1.5 K the directions of the magnetic moments differ because of the different anisotropy of the rare earth ions. Except for Tm and Yb (which does not order above 1.5 K), the magnetic moment of the R³⁺ cations are close to the free-ion value. The magnetic moment of Ni²⁺ is around 1.4 , the strong reduction with respect to the free-ion value is probably due to a combination of low-dimensional quantum effects and covalency. The thermal evolution of the magnetic structures from T _N down to 1.5 K is studied in detail. A smooth re-orientation, governed by the magnetic anisotropy of R³⁺, seems to occur below and very close to T _N in some of these compounds: the Ni moment rotates from nearly parallel to the a-axis toward the c-axis following the R moments. We demonstrate that for setting up the 3D magnetic ordering the R-R exchange interactions cannot be neglected. Received 19 July 2001     

Synthesis of tetrahydroisoquinolines through TiCl4-mediated cyclization and Et3SiH reduction

A versatile and efficient telescoped reaction sequence for the synthesis of tetrahydroisoquinolines(THIQs)is reported that uses TiCl4 to promote cyclization of a benzylaminoacetal derivative and Et3SiH for reduction of the intermediate 4-hydroxy-THIQ.This method is complimentary to the classical Pomeranz-Fritsch and related reactions since it tolerates electron-withdrawing substituents and allows access to 8-substituted THIQs.     

The dependence of the structural and optical properties on the Te mole fraction in ZnS1−xTex/GaAs heterostructures

Lattice-mismatched ZnS_1−xTe_x epilayers with various Te mole fractions on GaAs (100) substrates were grown by double well temperature gradient vapor deposition. X-ray diffraction patterns showed that the grown ZnS_1−xTe_x layers were epitaxial films. The photoluminescence spectra showed that the peak position of the acceptor-bound exciton (A⁰, X) varied dramatically with changing the Te mole fraction and that the behavior of the (A⁰, X) peak position of the ZnS_1−xTe_x epilayers with a small amount of the Te mole fraction was attributed to a bowing effect. The reflectivity and ellipsometry spectra showed that the absorption energy peak was significantly affected due to the Stoke's effect. These results provide important information on the structural and optical properties of ZnS_1−xTe_x/GaAs heterostructures for improving optoelectronic device efficiencies operating in the spectral range between near ultraviolet and visible regions.     

Luminescence properties of ZnSe films grown by hot wall epitaxy

Received: 10 June 1996/Accepted: 20 October 1996     

Two-dimensional zinc oxide nanostructure

Transparent two-dimensional ultralong and ultrabroad single crystal zinc oxide (ZnO) nanosheets were directly synthesized by a simple solid vapor deposition process under lead oxide (PbO) atmosphere. The nanosheets are well grown single crystals with thickness of about 50-70 nm, breadth of 50-100 μm and length of 4-6 mm. The growth mode of the ultrabroad nanosheets displays a unique aspect that (001) planes form the narrowest facets of the nanosheets, which is completely different from other belt-like nanostructures of ZnO. Control experiments show that PbO play an important role in the vapor-solid growth process of ZnO nanosheets.     

Magnetotransport properties of (La0.7Pb0.3MnO3)1−xAgx composites

Magnetic and transport properties of (La_0.7Pb_0.3MnO₃)_1−xAg_x composites are explored in this study. Ferromagnetism is gradually attenuated due to the magnetic dilution with increase of Ag content percentage. Clearly irreversible behavior in the zero-field cooling and field cooling curves at a low field caused by the competition between the magnetization and magnetic domain orientation processes has been observed as x increases. Saturation magnetization decreases as x increases, while ferromagnetic transition temperature remains around 346 K for all composites. The resistivity decreases significantly for (La_0.7Pb_0.3MnO₃)_1−xAg_x composites. It is suggested that introduction of Ag into the niche of grain boundaries forms artificial conducting network and improves the carriers to transport. However, enhancement of magnetoresistance has been observed for the system.     

Microscopic measurement of the linear compressibilities of two-dimensional fatty acid mesophases

The linear compressibility of two-dimensional fatty acid mesophases has been determined by grazing incidence X-ray diffraction. The unit cell parameters of the , , , S and phases of behenic acid and of the phase of myristic acid were determined as a function of surface pressure and temperature. Surface pressure versus molecular area isotherms were reconstructed from these measurements, and the linear compressibility (relative distortion along a given direction for a two-dimensional isotropic applied stress) was determined both in the sample plane and in a plane normal to the aliphatic chain director (transverse plane). The linear compressibilities range over two orders of magnitude from 0.1 to 10 m/N and are distributed depending on their magnitude in 4 different sets which we are able to associate with different molecular mechanisms. The largest compressibilities (10 m/N) are observed in the tilted phases. They are apparently independent on the chain length and could be related to the reorganization of the headgroup hydrogen-bounded network, whose role should be revalued. Intermediate compressibilities are observed in phases with quasi long-range order (directions normal to the molecular tilt in the or phases, S phase, and could be related to the ordering of these phases. The lowest compressibilities are observed in the solid untilted phase and for one direction of the S and phases. They are similar to the compressibility of crystalline polymers and correspond to the interactions between methyl groups in the crystal. Finally, negative compressibilities are observed in the transverse plane for the and phases and can be traced to subtle reorganizations upon untilting. Received: 29 July 1997 / Revised: 14 October 1997 / Accepted: 23 October 1997     

Magnetic dimensionality of Y(2−x)DyxBaCuO5

In this communication, we report the effect that doping Y₂BaCuO₅ with Dy has on its two-dimensional (2D) magnetic structure. Pure samples at both ends of the series, as well as samples doped with 1, 5, 10 and 25% dysprosium, have been characterised using X-ray diffraction, and AC susceptibility together with neutron diffraction studies on the 1 and 5% samples, which were used to measure the magnetic ordering at low temperatures. The results show that 1% Dy is enough to disrupt the 2D magnetic ordering turning it into a 3D array. The low dysprosium concentration indicates that the 3D ordering is achieved without the existence of a rare earth magnetic sublattice. The change in the ordering temperature from 27 K for the pure Y₂BaCuO₅ to 16 K for the 1 and 5% Dy compounds, together with the parameters from the AC susceptibility fittings, reveal that the effect of the Dy doping affects the electronic structure of the Cu ions that become involved in the superexchange pathways. The discrepancy between the parameters obtained by the Curie-Weiss fittings of the real part of the AC susceptibility and the neutron diffraction results, shows that the exchange mechanism deviates from the mean field model for all dysprosium concentrations.     

Mössbauer characterization of tin dopant ions in the antiferromagnetic ilmenite MnTiO3

Mössbauer parameters of ¹¹⁹Sn diamagnetic dopant cations in an antiferromagnetic compound having the ilmenite structure are for the first time reported. The spectra reveal a well resolved hyperfine splitting pattern of combined magnetic and quadrupole interactions (at 5 K, δ=0.19 mm/s, H₁=52.5 kOe, eV_ZZQ_3/2=−0.80 mm/s, θ≈0°). This spectral component whose contribution (A₁=82%) represents more than four fifths of the total amount of the dopant (Sn/(Mn+Ti)=1/200) is assigned to Sn(IV) ions located in the bulk of MnTiO₃, on the Mn(II) site, and with a Mn(II) vacancy in their nearest surrounding. Two spectral components with minor contributions are also observed: one of them (H₂≈25 kOe, A₂=8%) can be assigned to Sn(IV) ions, in the MnTiO₃ lattice as well, on a site where they exhibit a weaker spin polarization (this site could be the Ti(IV) one) and the other (H₃=0 kOe, A₃=10%) to SnO₂ or/and Ti_1−xSn_xO₂ clusters. The Néel temperature of MnTiO₃ probed by the ¹¹⁹Sn dopant (T_N=69±2 K) agrees well with the values previously provided by ESR and antiferromagnetic resonance measurements. Variation of H₁ with temperature follows close the Brillouin function for S=5/2. No perturbation appears in the Mössbauer spectra around T=90 K where a broad peak, characteristic of 2D magnetic interactions, is observed on the static magnetic susceptibility curve.     

Electronic, magnetic, and vibrational properties of the molecular magnet Mn4 monomer and dimer

A new type of the single-molecule magnet [Mn₄O₃Cl₄(O₂CEt)₃(py)₃] forms dimers. Recent magnetic hysteresis measurements on this single-molecular magnet revealed interesting phenomena: an absence of quantum tunneling at zero magnetic field and tunneling before magnetic field reversal. This is attributed to a significant antiferromagnetic exchange interaction between different monomers. To investigate this system, we calculate the electronic structure, magnetic properties, intramolecular and intermolecular exchange interactions using density-functional theory within the generalized-gradient approximation. Our calculations agree with experiment. We find that the calculated threefold symmetric structure is vibrationally stable. We also calculate vibrational infrared absorption and Raman scattering intensities for the monomer which can be tested experimentally.