Origin of Ferromagnetism and Magnetic Anisotropy in a Family of Copper(II) Triangles

Previously reported ferromagnetic triangles (NnBu₄)₂[Cu₃(μ₃-Cl)₂(μ-4-NO₂-pz)₃Cl₃] ( 1 ), (PPN)₂[Cu₃(μ₃-Cl)₂(μ-pz)₃Cl₃] ( 2 ), (bmim)₂[Cu₃(μ₃-Cl)₂(μ-pz)₃Cl₃] ( 3 ) and newly reported (PPh₄)₂[Cu₃(μ₃-Cl)₂(μ-4-Ph-pz)₃Cl₃] ( 4 ) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio calculations to assess the origins of their ferromagnetism and of the magnetic anisotropy of their ground S=3/2 state (PPN⁺=bis(triphenylphosphine)iminium, bmim⁺=1-butyl-3-methylbenzimidazolium, pz⁻=pyrazolate). Ab initio studies revealed the d character of the magnetic orbitals of the compressed trigonal bipyramidal copper(II) ions. Ferromagnetic interactions were attributed to weak orbital overlap via the pyrazolate bridges. From the wavefunctions expansions, the ratios of the magnetic couplings were determined, which were indeterminate by magnetic susceptometry. Single-crystal EPR studies of 1 were carried out to extend the spin Hamiltonian with terms which induce zero-field splitting (zfs), namely dipolar interactions, anisotropic exchange and Dzyaloshinskii–Moriya interactions (DMI). The data were treated through both a giant-spin model and through a multispin exchange-coupled model. The latter indicated that ≈62 % of the zfs is due to anisotropic and ≈38 % due to dipolar interactions. The powder EPR data of all complexes were fitted to a simplified form of the multispin model and the anisotropic and dipolar contributions to the ground state zfs were estimated.     

Influence of clay suspensions on the precipitation of CaCO3 in seawater

The effect of montmorillonite and kaolinite, most common clay in marine water, on nucleation and growth of calcium carbonate in standard sea water was studied. Crystallization was induced by the degasification of the dissolved carbonic gas. It was shown by XRD and SEM analysis that CaCO₃ crystallize under its aragonite polymorph some either the clay concentration or type. It was also found that tested clays inhibited significantly the crystallization of calcium carbonate, especially for concentrations higher than 25 mgL^–1. From the fine analyses of the formed solid, it was suggested that the tested clays have an indirect effect on nucleation and growth of aragonite by increasing the Mg ions concentration, strong inhibitor of CaCO₃ formation, in the neighbourhood of clay particles where supersaturation is the higher and than crystallization can occur. In addition to its indirect role, kaolinite can interact with aragonite by adsorbing on their faces and blocking growth sites (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the choice of explicit stabilizing terms in column generation

Column generation algorithms are instrumental in many areas of applied optimization, where linear programs with an enormous number of columns need to be solved. Although successfully employed in many applications, these approaches suffer from well-known instability issues that somewhat limit their efficiency. Building on the theory developed for nondifferentiable optimization algorithms, a large class of stabilized column generation algorithms can be defined which avoid the instability issues by using an explicit stabilizing term in the dual; this amounts at considering a (generalized) augmented Lagrangian of the primal master problem. Since the theory allows for a great degree of flexibility in the choice and in the management of the stabilizing term, one can use piecewise-linear or quadratic functions that can be efficiently dealt with using off-the-shelf solvers. The practical effectiveness of this approach is demonstrated by extensive computational experiments on large-scale Vehicle and Crew Scheduling problems. Also, the results of a detailed computational study on the impact of the different choices in the stabilization term (shape of the function, parameters), and their relationships with the quality of the initial dual estimates, on the overall effectiveness of the approach are reported, providing practical guidelines for selecting the most appropriate variant in different situations.     

Estimation and tests of independence in copula models via divergences

We introduce new estimates and tests of independence in copula models with unknown margins using ?-divergences and the duality technique. The asymptotic laws of the estimates and the test statistics are established both when the parameter is an interior point or not. To cite this article: S. Bouzebda, A. Keziou, C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

Vector subspaces and operators with the Stone condition

We introduce the notion of an operating function on a subset of a F{\Phi} -algebra E. Then we use this notion to generalize results from Huijsmans and de Pagter (Proc. Lond. Math. Soc. 48:161–174, 1984) about the connection between vector subspaces and subalgebras of E. In the second part we investigate the analogous problem for operators.     

Hierarchical porous carbon with designed pore architecture and study of its adsorptive properties

Ordered mesoporous carbon nanoparticles have been synthesized by a nanocasting procedure from furfuryl alcohol impregnation into alumino–silica UVM-7 material. By a proper adjustment of the synthesis parameters, furfuryl alcohol volume vs. template pore volume, it was possible to obtain a carbonaceous templated material which keeps the hierarchical bimodal porosity of the silica together with its high surface area (>1000 m²/g), as it was confirmed by means of electron transmission microscopy and N₂ adsorption isotherms. This carbon material was evaluated by testing it as a sorbent for several pesticides in aqueous solutions. Its absorption efficiency was compared with typical commercial solid phase extraction materials such as silica C₁₈ and graphitized carbon black GCB.