Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and (19)F, (121)Sb, and (123)Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl(4)(+)Sb(OTeF(5))(6)(-) and SbBr(4)(+)Sb(OTeF(5))(6)(-)

The stable salts, SbCl(4)(+)Sb(OTeF(5))(6)(-) and SbBr(4)(+)Sb(OTeF(5))(6)(-), have been prepared by oxidation of Sb(OTeF(5))(3) with Cl(2) and Br(2), respectively. The SbBr(4)(+) cation is reported for the first time and is only the second example of a tetrahalostibonium(V) cation. The SbCl(4)(+) cation had been previously characterized as the Sb(2)F(11)(-), Sb(2)Cl(2)F(9)(-), and Sb(2)Cl(0.5)F(10.5)(-) salts. Both Sb(OTeF(5))(6)(-) salts have been characterized in the solid state by low-temperature Raman spectroscopy and X-ray crystallography. Owing to the weakly coordinating nature of the Sb(OTeF(5))(6)(-) anion, both salts are readily soluble in SO(2)ClF and have been characterized in solution by (121)Sb, (123)Sb, and (19)F NMR spectroscopy. The tetrahedral environments around the Sb atoms of the cations result in low electric field gradients at the quadrupolar (121)Sb and (123)Sb nuclei and correspondingly long relaxation times, allowing the first solution NMR characterization of a tetrahalocation of the heavy pnicogens. The following crystal structures are reported: SbCl(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.022(1) ?, c = 18.995(4) ?, V = 1652.3(6) ?(3), D(calc) = 3.652 g cm(-)(3), Z = 2, R(1) = 0.0461; SbBr(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.206(1) ?, c = 19.297(3) ?, V = 1740.9(5) ?(3), D(calc) = 3.806 g cm(-)(3), Z = 2, R(1) = 0.0425. The crystal structures of both Sb(OTeF(5))(6)(-) salts are similar and reveal considerably weaker interactions between anion and cation than in previously known SbCl(4)(+) salts. Both cations are undistorted tetrahedra with bond lengths of 2.221(3) ? for SbCl(4)(+) and 2.385(2) ? for SbBr(4)(+). The Raman spectra are consistent with undistorted SbX(4)(+) tetrahedra and have been assigned under T(d)() point symmetry. Trends within groups 15 and 17 are noted among the general valence force constants of the PI(4)(+), AsF(4)(+), AsBr(4)(+), AsI(4)(+), SbCl(4)(+) and SbBr(4)(+) cations, which have been calculated for the first time, and the previously determined force constants for NF(4)(+), NCl(4)(+), PF(4)(+), PCl(4)(+), PBr(4)(+), and AsCl(4)(+), which have been recalculated for the P and As cations in the present study. The SbCl(4)(+) salt is stable in SO(2)ClF solution, whereas the SbBr(4)(+) salt decomposes slowly in SO(2)ClF at room temperature and rapidly in the presence of Br(-) ion and in CH(3)CN solution at low temperatures. The major products of the decompositions are SbBr(2)(+)Sb(OTeF(5))(6)(-), as an adduct with CH(3)CN in CH(3)CN solvent, and Br(2).     

Analogie Photochimique. II—Cyclisation des Aldéhydes δ,ε Insaturés sous Impact Electronique

The mass spectra of 4, 4-dimethyl δε-unsaturated aldehydes show an ion at m/e 126 which results from the elimination of a neutral olefin directly from the molecular ion. This fragmentation is shown to occur through a cyclohexanone intermediate involving a process whcih has its equivalent in the photochemistry of these aldehydes. The abundance ratios of the unimolecular metastable decompositions of these m/e 126 ions are in excellent agreement with the proposed mechanism.     

Novel fused D-A dyad and A-D-A triad incorporating tetrathiafulvalene and p-benzoquinone

Novel fused donor-acceptor dyad (TTF-Q or D-A) and acceptor-donor-acceptor triad (Q-TTF-Q or A-D-A) incorporating the donor tetrathiafulvalene (TTF) and the acceptor p-benzoquinone (Q) have been synthesized. The solution UV-vis spectra of these molecules display a low-energy absorption band that is attributed to an intramolecular charge transfer between both antagonistic units. The presence of reversible oxidation and reduction waves for the donor and acceptor moieties was shown by cyclic voltammetry, in agreement with the ratio TTF/quinone(s) units. The successive generation from these compounds of the cation radical and anion radical obtained upon (electro)chemical oxidation and reduction, respectively, was monitored by optical and ESR spectroscopies. The anion radical Q-TTF-Q(-.) triad was demonstrated to be a class II mixed-valence system with the existence of a temperature-dependent intramolecular electron transfer. The crystallographic tendency of these fused systems to overlap in mixed stacks of alternating A-D-A units is also discussed.     

Growth and characterization of titanium suboxide crystals

The titanium and vanadium suboxides MO_x (where 1.5 < x < 2 and M is Ti or V) are particularly interesting compounds because many show metal-insulator transitions which result in interesting electrical, magnetic and spectroscopic phenomena. We have grown high purity crystals of the congruently melting compounds Ti₂O₃, Ti₃O₅ and V₂O₃ and mixed compounds using the tri-arc melting technique. Crystals were grown at speeds of 1-1.5 cm/h. The Magneli phases M_nO_2n-1 (n?4) do not melt congruently and therefore we have grown a number of these compounds using chemical vapor transport with TeC1₄ or NH₄C1. Twinned needles typically larger than 1 cm long are grown by pulling transport in 3–5 days. The crystals have been characterized by X-ray diffraction, atomic absorption and gamma-ray activation analysis. In addition, the use of a scanning microcalorimeter made it possible to determine phase transitions on needles weighing as little as 2–10 mg. The stoichiometry was determined using X-ray diffraction, pycnometric density measurements and thermogravimetry.     

Preparation of polyimide/silica hybrid material by sol–gel process under basic catalysis: Comparison with acid conditions

Hybrid polyimide/silica materials were prepared from polyimides bearing reactive functions along the polymer backbone, which can react with. The silica phase was formed by sol–gel process using ammonium hydroxide catalyst. Silica fillers prepared under basic conditions were compared with materials prepared using chlorhydric acid. The synthesized hybrid materials were characterized by TGA, IRTF, and NMR. The density of the different systems was also measured. The morphology of these hybrid systems were investigated by both scanning and transmission electron microscope. Thermal properties of the composites were also evaluated by DSC and DMA. The morphology of silica fillers highly depends on the catalyst, on the reaction conditions of the sol–gel process, and the linking formation with the polyimide. It results that optimized conditions lead to homogeneous hybrid films containing 12 wt % of silica particles of about 20 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1891–1902, 2008     

Strong polynomiality of resource constraint propagation

Constraint-based schedulers have been widely successful in tackling complex, disjunctive, and cumulative scheduling applications by combining tree search and constraint propagation. The constraint-propagation step is a fixpoint algorithm that applies pruning operators to tighten the release and due dates of activities using precedence or resource constraints. A variety of pruning operators for resource constraints have been proposed; they are based on edge finding or energetic reasoning and handle a single resource.

Complexity results in this area are only available for a single application of these pruning operators, which is problematic for at least two reasons. On the one hand, the operators are not idempotent, so a single application is rarely sufficient. On the other hand, the operators are not used in isolation but interact with each other. Existing results thus provide a very partial picture of the complexity of propagating resource constraints in constraint-based scheduling.

This paper aims at addressing these limitations. It studies the complexity of applying pruning operators for resource constraints to a fixpoint. In particular, it shows that: (1) the fixpoint of the edge finder for both release and due dates can be reached in strongly polynomial time for disjunctive scheduling; (2) the fixpoint can be reached in strongly polynomial time for updating the release dates or the due dates but not both for the cumulative scheduling; and (3) the fixpoint of “reasonable” energetic operators cannot be reached in strongly polynomial time, even for disjunctive scheduling and even when only the release dates or the due dates are considered.     

Die Titrirung der Phosphors?ure im Harn mit Uranl?sung

Ohne Zusammenfassung     

Electronic excitations during grazing scattering of hydrogen atoms on KI(001) and LiF(001) surfaces

The energy loss of hydrogen atoms with energies of 400 eV and 1 keV is studied in coincidence with the number of emitted electrons during grazing scattering from atomically clean and flat KI(001) and LiF(001) surfaces. The energy loss spectra for specific numbers of emitted electrons are analyzed in terms of a binary interaction model based on the formation of transient negative ions via local capture of valence band electrons from anion sites. Based on computer simulations we derive for this interaction scenario probabilities for the production of surface excitons, for electron loss to the conduction band of KI, for emission of electrons, and for formation of negative hydrogen ions. The pronounced differences of data obtained for the two surfaces are attributed to the different electronic structures of KI and LiF.     

14.5GHz紧凑型、低成本、全永磁ECR离子源

A compact 14.5GHz electron cyclotron resonance (ECR) ion source for the production of slow, multiply charged ions has been constructed,with the plasma-confining magnetic field produced exclusively by permanent magnets.Microwave power of up to 175W in the frequency range from 12.75 to 14.SGHz is transmitted from ground potential via a PTFE window into the water-cooled plasma chamber which can be equipped with an aluminum liner.The waveguide coupling system serves also as biased electrode,and two remotely-controlled gas inlet valves connected via an insulating break permit plasma operation in the gas- mixing mode.A triode extraction system sustains ion acceleration voltages between 1kV and 10kV.The ECR ion source is fully computer-controlled and can be remotely operated from any desired location via Ethernet.