Characterization of new-layered Cr(III)-doped chlorocadmiumphosphate, Cd(HPO4)Cl·[H3N(CH2)6NH3]0.5 crystal by EPR and optical studies

Cr(III)-doped Cd(HPO₄)Cl·[H₃N(CH₂)₆NH₃]_0.5, a new-layered cadmium phosphate, is synthesized in acidic condition at room temperature. EPR and optical studies are carried out at room temperature. Polycrystalline EPR spectrum reveals the presence of two sites of Cr(III) ions in this layered phosphate lattice with zero-field splitting values of 24.24 and 7.65 mT, indicating that Cr(III) ions are in distorted octahedral sites. The optical absorption spectrum of the sample indicates near octahedral symmetry for the dopant ions. Crystal field, inter-electronic and bonding parameters are evaluated by collaborating EPR and optical data. The evaluated parameters suggest the mode of entry of Cr(III) ion into the layered phosphate as interstitial site, and bonding between the metal and ligand is partially covalent.     

Spin-peierls transition in dimerized stacks of anion-radical salt (N-Me-2,5-di-Me-Pz)(TCNQ)2, (Pz is pyrazine)

An anion-radical salt (ARS) (N-Me-2,5-di-Me-Pz)(TCNQ)₂, where Pz is pyrazine, was synthesized and its crystal structure was resolved. X-ray diffraction experiments on single crystals were performed. Heat capacity was measured in the temperature range from 2 to 300 K. Magnetisation and magnetic susceptibility were measured in the temperature range from 2 to 300 K and the low-temperature part was measured in magnetic fields from 5 mT to 5 T. The experimental results were explained in terms of dimerized Heisenberg spin chain model. Numerical calculations were performed and compared with experimental data.     

Decay of the neutron-rich isotope 113Ru to 113Rh

The decay of neutron-rich isotope ¹¹³Ru obtained as on-line mass separated product of proton-induced fission has been investigated by γγ coincidence and spectrum multiscaling measurements. Decay schemes for both low- and high-spin isomers of ¹¹³Ru have been constructed. The level scheme of ¹¹³Rh is considerably extended. Systematics of the lowest-lying rhodium levels is smooth. The picture of shape coexistence established for neutron-rich Rh isotopes near-neutron midshell is confirmed with the observation of a K = 1/2 deformed band, with its 3/2⁺ state at 600 keV being the lowest-lying level and of probable 7/2⁺ and 5/2⁺ band members. A large fraction of β feeding is found to populate high-lying levels in ¹¹³Rh. The GT strength in ¹¹³Ru^m decay is significantly larger than for the decay of ¹¹³Ru_g and of lighter rhodium isotopes. Received: 18 January 2001 / Accepted: 14 January 2002     

Heavy-element chemistry --Status and perspectives

In the past ten years, nuclear chemists have made considerable progress in developing fast on-line separation techniques, which allowed to chemically characterize the first four transactinide elements Rf (rutherfordium, Z = 104), Db (dubnium, Z = 105), Sg (seaborgium, Z = 106), and recently also Bh (bohrium, Z = 107). In all cases the isolated nuclides were unambiguously identified by observing genetically linked decay chains. Nuclides with production cross-sections of less than 100 pb and half-lives as short as a few seconds have been chemically isolated. Thus, chemists have discovered or significantly contributed to the characterization of the nuclear-decay properties of a number of transactinide nuclei. New techniques with greatly improved overall efficiencies should allow chemists to extend their studies to even heavier elements such as Hs (hassium, Z = 108) and to the recently discovered superheavy elements with Z = 112 and 114, which can be produced only with picobarn cross-sections. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: andreas.tuerler@psi.ch     

Low-temperature property investigation of the lead indium-niobate-lead nickel-niobate solid solution

The complex perovskite solid solution (1−x) Pb(In_1/2Nb_1/2)O₃-(x) Pb(Ni_1/3Nb_2/3)O₃ has been successfully prepared by the Columbite precursor method. The temperature dependencies of the dielectric constant and pyroelectric coefficient were measured between −261 and 200 °C. Relaxor ferroelectric behavior has been noticed in all compositions across the solid solution. The room-temperature electrostrictive coefficient, Q₃₃, was 1.83×10⁻² C²/m⁴ for x=0.10. No room-temperature piezoelectric activity was detected; however, upon cooling to −261 °C the maximum coupling coefficients k_p=29%, k_t=11%, and k₃₃=31% were observed for the composition x=1.00.     

Phase diagram for stripes in YBa2Cu3O6+x superconductors

Neutron scattering has been used to measure the charge and spin structure in the YBa₂Cu₃O_6+x superconductors. Incommensurate static charge ordering is found at low doping levels while only charge fluctuations are found at higher doping. The spin structure is complex with both a commensurate resonance and incommensurate structure observed at low temperatures. The scattering results are used to construct a phase diagram for stripes in the YBa₂Cu₃O_6+x system.     

Enhanced gas-sensing behaviour of Ru-doped SnO2 surface: A periodic density functional approach

A theoretical study on Ru-doped rutile SnO₂(1 1 0) surface has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA-RPBE) level with a periodic supercell approach. Electronic structure analysis was performed based on the band structure and partial density of states. The results provide evidence that the electronic structures of SnO₂(1 1 0) surface are modified by the surface Ru dopant, in which Ru 4d orbital are located at the edge of the band gap region. It is demonstrated that molecular oxygen adsorption characteristics on stoichiometric SnO₂(1 1 0) surface are changed from endothermic to exothermic due to the existence of surface Ru dopant. The dissociative adsorption of molecular oxygen on the Ru_5c/SnO₂(1 1 0) surface is exothermic, which indicates that Ru could act as an active site to increase the oxygen atom species on SnO₂(1 1 0) surface. Our present study reveals that the Ru dopant on surface is playing both electronic and chemical role in promoting the SnO₂ gas-sensing property.     

Microwave-assisted synthesis of flower-like and leaf-like CuO nanostructures via room-temperature ionic liquids

Flower-like and leaf-like cupric oxide (CuO) single-crystal nanostructures have been successfully synthesized using ionic liquid 1-octyl-3-methylimidazolium trifluoroacetate ([Omim]TA) under the microwave-assisted approach. By controlling the concentration of [Omim]TA and reaction temperature, shape transformation of CuO nanostructures could be achieved in a short period of time. The results indicate that ionic liquid [Omim]TA plays an important role in the formation of different morphologies of CuO crystals. The crystal structure and morphology of products were characterized by X-ray powder diffraction (XRD), infrared spectrum (IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), and selected-area electron diffraction (SAED). A possible mechanism for CuO nanostructure was proposed. In addition, UV-vis spectroscopy was employed to estimate the band gap energies of CuO crystals.     

Shape-dependent local internal stress of α-Cr2O3 nanocrystal fabricated by pulsed laser ablation

The α-Cr₂O₃ single-crystal nanocondensates were fabricated by pulsed laser ablation in air and characterized by analytical electron microscopy regarding shape-dependent local internal stress of the anisotropic crystal. The nanocondensates formed predominantly as rhombohedra with well-developed surfaces and occasionally hexagonal plate with thin edges and blunt corners. Such nanocondensates showed Raman shift for the CrO₆ polyhedra, indicating a local compressive stress up to ca. 4 GPa on the average. Careful analysis of the lattice fringes revealed a local compressive stress (0.5% strain) at the thin edge of the hexagonal plates and a local tensile stress (0.3–1.0% strain) near the relaxed , , and (0 0 0 1) surfaces of truncated rhombohedra. The combined effects of nanosize, capillarity force at sharp edge, and specific surface relaxation account for the retention of a local internal compressive stress built up in an anisotropic crystal during a very rapid heating–cooling process.     

Nanoscale formation mechanism of conducting filaments in NiO thin films

We have studied the nanoscale electrical properties of NiO thin films by using conducting atomic force microscopy (CAFM) to understand the mechanism of resistance change of the NiO thin films as we changed the applied voltage. We observed that inhomogeneous conducting filaments were generated by external voltage bias; in addition, some of the inhomogeneous conducting filaments were durable while some of them were not, and they disappeared. We deduced that the resistance change of the NiO thin films was related to inhomogeneous filamentary conducting paths generated by both Ni ions in thermodynamically unstable NiO and the existence of conducting filament segments generated by high voltage bias.