BEBO Calculations for hydrogen abstraction by 0(3P)

Rate constants for hydrogen transfer reactions from C—H bonds to O(³P) in the gas phase have been calculated by the bond-energy bond-order method. The use of a single or double triplet repulsion term is discussed. Computational results indicate that with carefully selected input parameters, it is unnecessary to use a double-repulsion term. Tunneling corrections were carried out by two different procedures. Results indicate that in this case there is not much difference between the simple Wigner's treatment and more complicated methods.     

Approximation de quelques problèmes de type Stokes par une méthode d'éléments finis mixtes

Résumé Nous présentons dans cet article une méthode d'éléments finis mixtes qui permet la résolution des équations de Stokes avec des conditions aux limites de type Fourier ou Neumann. Pour cette méthode nous démontrons que les estimations de l'erreur d'approximation sont optimales; en vitesse et en pression. Ces résultats de convergences généralisent à ce type non standard de conditions aux limites les travaux de Glowinski-Pironneau [9, 10] pour le probleme de Stokes avec des conditions aux limites de Dirichlet.

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Mixed-finite element approximation of stokes type problems

Summary We present in this paper a mixed-finite element approximation of Stokes equations with boundary conditions of Fourier's or Neumann's type. For this approximation we prove that the error estimates for the velocity-vector and for the pressure are optimal. These results of convergence generalize to this kind of boundary conditions the Glowinski-Pironneau's approximation of Stokes problem with Dirichlet's boundary conditions [9, 10].

     

Direct determination of nickel in gas oil by atomic absorption spectrometry with electrothermal atomization

A rapid graphite-furnace atomic absorption procedure with simple dilution of samples was tested for the direct determination of sub-ppm levels of nickel in gas oils. The selection of appropriate graphite-furnace parameters, the type of solvent and organometallic standard, the effect of gas oil concentration in diluted samples, precision, accuracy and detection limit were investigated. Sample dilution was necessary because of high viscosity. Results obtained by standard addition for heavy gas oils were confirmed by a wet-ashing flame atomic absorption procedure. The relative standard deviation (r.s.d.) for consecutive determinations of nickel in gas oil solution containing 19 μg Ni l^?1 was 3.1%, and day-to-day r.s.d. for a reference gas oil sample was 5.3%. Accuracy was determined with an NBS standard reference oil GM-5 (4.6 ± 4.7% relative error in four determinations). Recovery experiments gas 104 ± 12% of the added nickel.     

Au and Cu Atoms on NaCl(001): a single-atom based memory device prototype?

We present a first-principle study of gold and copper atoms adsorbed in NaCl(001) surfaces. Motivated by a recent STM experiment on this subject, the electronic and magnetic properties of Au and Cu atoms are investigated, as well as the modifications in these properties under charge injection. Similarities of these systems and the corresponding isolated atom are exploited. A discussion about the possibility of applying the studied systems on high-density memory devices is addressed.     

Nuclear shadowing in Glauber–Gribov theory with Q 2-evolution

We consider deep inelastic scattering off nuclei in the Regge limit within the Glauber–Gribov model. Using unitarized parton distribution functions for the proton, we find sizeable shadowing effects on the nuclear total and longitudinal structure functions, $F_{2}^{A}$ and $F_{L}^{A}$ , in the low-x limit. Extending a fan-diagram analysis for the large-mass region of coherent diffraction off nuclei to high Q ², we also find significant shadowing effects in this kinematical regime. Finally, we discuss the shortcomings of our approach and possible extensions of the model to other kinematical regimes.     

The trace of totally positive algebraic integers

For all totally positive algebraic numbers except a finite number of explicit exceptions, the following inequality holds:

\max(1.780022,1.66+\alpha_1), \end{displaymath}">

where is the degree of and its conjugates. This improves previous results of Smyth, Flammang and Rhin.

     

A new class of estimators of a “scale” second order parameter

For a large class of heavy-tailed distribution functions F in the domain of attraction for maxima of an Extreme Value distribution with tail index γ>0, the function A(t), controlling the speed of convergence of maximum values, linearly normalized, towards a non-degenerate limiting random variable, may be parameterized as , ρ < 0, β∈ℝ, where β and ρ are second order parameters. The estimation of ρ, the “shape” second order parameter has been extensively addressed in the literature, but practically nothing has been done related to the estimation of the “scale” second order parameter β. In this paper, and motivated by the importance of a reliable β-estimation in recent reduced bias tail index estimators, we shall deal with such a topic. Under a semi-parametric framework, we introduce a class of β-estimators and study their consistency. We deal with the conditions enabling us to get the asymptotic normality of the members of this class, and we illustrate the behaviour of the estimators, through Monte Carlo simulation techniques. Research partially supported by FCT / POCTI and POCI / FEDER.     

Rhenium complexes of tris(pyrazolyl)methanes and sulfonate derivative

The trioxo [ReO(3){SO(3)C(pz)(3)}] (1) (pz = pyrazolyl) and oxo [ReOCl{SO(3)C(pz)(3)}(PPh(3))]Cl (2) compounds with tris(pyrazolyl)methanesulfonate were obtained by treatment of Re(2)O(7) or [ReOCl(3)(PPh(3))(2)], respectively, with Li[SO(3)C(pz)(3)], whereas [ReCl(3){HC(pz)(3)}] (3), [ReCl(3){HC(3,5-Me(2)pz)(3)}] (4) and [ReCl(4){eta(2)-HC(pz)(3)}] (5) were prepared by reaction of [ReOCl(3)(PPh(3))(2)] (3,4) or [ReCl(4)(NCMe)(2)] (5) with hydrotris(pyrazolyl)methane HC(pz)(3) (3,5) or hydrotris(3,5-dimethyl-1-pyrazolyl)methane HC(3,5-Me(2)pz)(3) (4). [ReO{SO(3)C(pz)(3)}{OC(CH(3))(2)pz}][ReO(4)] 6, with a chelated pyrazolyl-alkoxide, was derived from an unprecedented ketone-pyrazolyl coupling on reaction of crude 1 with acetone. The compounds have been characterized by elemental analyses, IR and NMR spectroscopies, FAB-MS spectrometry and cyclic voltammetry and, in the case of 5 and 6, also by single-crystal X-ray diffraction. The electrochemical E(L) Lever parameter has been estimated, for the first time, for the SO(3)C(pz)(3)(-) and oxo ligands allowing the measurement of their electron-donor character and comparison with other ligands. Compounds 1, 2 and 6 appear to be the first tris(pyrazolyl)methanesulfonate complexes of rhenium to be reported.     

Dynamic equilibrium between cyclic oligomers. Thermodynamic and structural characterization of a square and a triangle

A dynamic equilibrium has been found in CDCl3 between a neutral molecular square, [cis-Mo2(DAniF)2]4(O2CC6F4CO2)4 (1) and triangle, [cis-Mo2(DAniF)2]3(O2CC6F4CO2)3 (2) (DAniF = the anion of N,N'-di-p-anisylformamidine). The two components have been crystallographically characterized and solution studies by 1H and 19F NMR spectra of the concentration- and the temperature-dependence of the equilibrium have been performed. The conversion of three moles of molecular squares 1 to four moles of molecular triangles 2 has an equilibrium constant of 1.98(7) x 10(-4) at 23.7 degrees C. At this temperature, the DeltaG(0) for the conversion of three moles of squares to four moles of triangles is 21.0 kJ mol(-1). The conversion is enthalpically disfavored (DeltaH(0) = 23.5 kJ mol(-1)), but entropically favored (DeltaS(0) = 8.2 J K(-1) mol(-1)).