A new family of heavy transition metal coordination compounds and its application,I. Design,synthesis and characterization of volatile organohafnium precursors

The first three representatives of a new family of volatile organohafnium compounds suitable as metallo-organic chemical vapour deposition precursors were synthesized. A combination of cyclopentadienyl and alkoxo-ligands with a bicyclo[2.2.1]heptanc framework was used. Volatility at relatively low temperatures for hafnium compounds was found and the precursors were characterized by elemental analysis and spectroscopic methods (IR, ¹H and ¹³C NMR, mass spectrometry and mass-analysed ion kinetic energy spectroscopy). The outlook for use in hafnium functional materials synthesis was derived from the fragmentation data.     

Structural and infrared spectroscopic characterization of Co6C(CO)12S2: a high-nuclearity carbido carbonyl cluster spontaneously formed from dicobalt octacarbonyl and carbon disulphide

Co₆C(CO)₁₂S₂ (I) has been isolated in crystalline form from the mixture of more than a dozen of carbonyl products formed when Co₂(CO)₈ reacts at room temperature with CS₂. Crystals of I are monoclinic with space group Cc, and lattice constants a  16.250(5), b  9.413(4), c  16.036(5) Å, β  116.77(4)°. Structure refinement gave R  0.034 for 1974 reflections. The CCo₆S₂ core of the molecule possesses idealized D_3h geometry. It is composed of a Co₆ trigonal prism, enclosing a C atom in the centre, and the triangular faces are capped symmetrically by the two S atoms. The core contains two sorts od CoCo distances: short one (2.432 Å) along the triangular edges, and long ones (2.669 Å) along the lateral edges. The average CoC distance is 1.94 Å, and the average CoS distance 2.192 Å.¹³CO-enriched samples were prepared photochemically and their IR spectra used in the assignment of the CO stretching frequencies. The CO stretching force constant was calculated to be 1670(2) Nm^-1.By the use of ¹³CS₂, I has also been obtained in a selectively carbido-¹³C-labelled form. The vibrational frequencies of the carbide atom were observed, and that at 819 cm^-1 (¹³C: 790 cm^-1) assigned to the species

, and that at 548 cm^-1 (¹³C: 535.5 cm^-1) to species E′. For the Co-C(carbide) force constant a value of 155 Nm^-1 was calculated. The cobalt—sulphur stretching frequencies were found at 309 cm^-1 (

) and 239 cm^-1 (E′). The CoS stretching force constant, 78 Nm^-1, is considerably lower than that obtained for SCo₃-(CO)₉, viz. 112 Nm^-1.     

Phase variation experiments in non-contact dynamic force microscopy using phase locked loop techniques

This work presents constant amplitude Dynamic Force Microscopy (DFM) measurements under ultra-high vacuum conditions performed with home-built digital electronics based on the principle of phase locked loop (PLL) techniques. In DFM so-called topography is often measured in constant frequency shift (Δf) mode. This study describes the influence of phase shifts on constant Δf imaging. Therefore, phase variation experiments were acquired, leading to information about the cantilever resonance behaviour close to the surface. As sample, an evaporated thin film of NaCl on a Cu(111) substrate was chosen in order to obtain a heterogeneous system with clean Cu and NaCl areas. The atomic structure of both materials was resolved, which is the first time true atomic resolution was obtained on a metal. Large apparent topography variations are observed on this heterogeneous sample when changing the phase between the excitation and oscillation of the cantilever end. Such artefacts can be explained by comparison with phase variation experiments.     

Statistical properties of corporate board and director networks

The boards of directors of the largest corporations of a country together with the directors form a dense bipartite network. The board network consists of boards connected through common directors. The director network is obtained taking the directors as nodes, and a membership in the same board as a link. These networks are involved in the decision making processes relevant to the macro-economy of a country. We present an extensive and comparative analysis of the statistical properties of the board network and the director network for the first 1000 US corporations ranked by revenue (Fortune 1000) in the year 1999 and for the corporations of the Italian Stock Market. We find several common statistical properties across the data sets, despite the fact that they refer to different years and countries. This suggests an underlying universal formation mechanism which is not captured in a satisfactory way by the existent network models. In particular we find that all the considered networks are Small Worlds, assortative, highly clustered and dominated by a giant component. Several other properties are examined. The presence of a lobby in a board, a feature relevant to decision making dynamics, turns out to be a macroscopic phenomenon in all the data sets.Received: 21 February 2004, Published online: 14 May 2004PACS: 87.23.Ge Dynamics of social systems - 89.65.-s Social and economic systems - 89.65.Gh Economics, econophysics, financial markets, business and management     

Effect of Surface Structure on Behavior of RuO2 Electrodes in Sulfuric Acid Aqueous Solution

The electrochemical properties of RuO₂ electrodes are studied by means of cyclic voltammetry, potential step, and impedance measurements in aqueous 0.5 mol/dm³ H₂SO₄ as a supporting electrolyte solution and applying the hanging electrolyte meniscus technique. Two types of the electrodes are used: bulk as-grown single-crystal having (101) exposed interface and 500 nm film produced by reactive RF magnetron sputtering at 450°C. The surface structure of the RuO₂ electrodes prepared by different techniques is defined from X-ray LAUE backscattering. Experimental data show that, for both RuO₂ electrodes, the charging components include a slow diffusion-controlled contribution, due to proton injection–ejection. The diffusion characteristics and the diffusion coefficients for the same electrodes are estimated and reported.     

Distribution of 210Pb and 137Cs in Snow and Soil Samples from Antarctica

Abstract

This paper reports some results on natural and artificial radionuclide distribution in snow samples collected at the Priestly Nevé—Plateau (inland, 1998 m a.s.l.) and the Vegetation Island (near the coast, 200 m a.s.l.) stations, and in a soil sample from Wood Bay station, both near the Italian Base at Terranova Bay in Antarctica. Data on Pb-210 and Cs-137 in snow samples from an 80 cm deep trench and in granulometric fractions of a soil core are discussed.     

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 μM; dynamic range: 2-200 μM, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: ±7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.