Ground state and response properties of mercury clusters

The change of the cohesive energy and the optical absorption spectra of small singly sized Hg clusters is discussed. The cohesive energy allows one to determine the different regimes of chemical bonding. The optical spectra show an abrupt transition to a collective, plasmon-like absorption as a function of increasing cluster size. The position of the one plasmon peak is: 1) independent of the charge state, 2) nearly independent of cluster size, and 3) agrees with that of the classical Mie plasmon calculated from the experimental dielectric constants. The width of the plasmon peaks is discussed. A strong influence of electronic correlations on the cluster size dependence of the oscillator strength is observed.     

Über die umsetzung von N-fluorsulfonylisocyanat mit verschiedenen phosphorverbindungen

Zusammenfassung N-Fluorsulfonylisocyanat bildet mit Triphenylphosphin, Phosphorigsäuretrisdimethylamid und Phosphorigsäuretriäthylester 11-Addukte unterschiedlicher Stabilität. Die Bildung von N-Fluorsulfonylcarbodiimiden aus N-Fluorsulfonylisocyanat und dem Phospholenoxid 7 gelingt nicht, da die Reaktion auf der Stufe des N-Fluorsulfonylphospholenimins stehenbleibt.

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Reaction of N-fluorosulfonyl isocyanate with phosphorus compounds

11-adducts of different stability are the products of the interaction of N-fluorosulfonylisocyanate with triphenylphosphine, phosphorous acid tris(dimethylamide), and triethyl phosphite. No N-fluorosulfonylcarbodiimides are formed from N-fluorosulfonylisocyanate and phospholene oxide (7), since the reaction does not proceed beyond the intermediate N-fluorosulfonylphospholene imine.

     

Comparison of a modified Kjeldahl and a vacuum fusion technique for determination of nitrogen in tantalum alloys

Results obtained for the determination of nitrogen in the tantalum alloys T-111 (Ta-8 W-2 Hf) and T-222 (Ta-10 W-2.5 Hf-0,1C) by Kjeldahl and vacuum fusion procedures are compared. Results obtained by each technique are shown for the determination of nitrogen m the MAB T-111 sample, two commercial T-111 samples and a commercial sample of T-222 alloy. In the 5-25 ppm range, the relative standard deviation was 3-9% by the Kjeldahl procedure and 4-8% by vacuum fusion. This is a measure of the homogeneity of the material as well as of the reproducibility of the results. The agreement of the results obtained by these two techniques increases confidence in the vacuum fusion results for nitrogen in tantalum.     

Structural investigations of tungsten silver phosphate glasses by solid state NMR, vibrational and X-ray absorption near edge spectroscopies

Glasses were prepared in the pseudo-binary system (1 − x)AgPO₃-xWO₃ (0≤ × ≤ 0.6 mol%). The structural evolution of the vitreous network was studied as a function of composition by thermal analysis, Fourier Transform Infrared spectroscopy (FTIR), Raman scattering, high resolution ³¹P solid state NMR and XANES at the W-L₁ absorption edge. For compositions with x ranging from 0 to 0.5 a pronounced increase in the glass transition temperature is observed, suggesting a significant increase in the glass network connectivity. At the same time Raman spectra indicate that tungsten atoms are linked to non-bridging oxygen atoms (W-O- or W=O bonded species) whereas the ³¹P MAS-NMR spectra indicate the successive formation of new P-O-W linkages. The formation of some anionic tungsten sites (if these are revealed by the presence of W-O terminal bonds) implies an increase in the average degree of polymerization of the phosphate network, which is consistent with the compositional evolution of the ³¹P MAS-NMR spectra at low x values. For higher x-values, the Raman spectra indicate the presence of W-O-W linkages. W-L₁ XANES data indicate that at least 90% of tungsten atoms are octahedrally coordinated.     

Aggregation Behavior of a Six‐Membered Cyclic Frustrated Phosphane/Borane Lewis Pair: Formation of a Supramolecular Cyclooctameric Macrocyclic Ring System

A new six‐membered cyclic frustrated phosphane/borane Lewis pair was liberated from its HB(C₆F₅)₂ adduct by treatment with vinylcyclohexane. The system is an active frustrated Lewis pair that undergoes cycloaddition reactions with suitable π reagents and it splits dihydrogen. At room temperature in solution the new compound is a monomer, however, in the crystal and in solution at low temperature it aggregates to a thermodynamically favoured supramolecular macrocyclic cyclooctamer.     

Ultralow quantum-defect eye-safe Er:Sc2O3 laser

Resonantly pumped Er(3+):Sc(2)O(3) laser operation is achieved with a quantum defect (QD) of 1.5% at liquid nitrogen temperature. The laser, in-line pumped at 1535 nm, operated at 1558 nm with a slope efficiency of over 45%. This is believed to be the lowest QD eye-safe laser ever reported. CW output of over 3.3 W was obtained in this first experiment.     

A fluorescence technique for measurement of slot injected fluid concentration profiles in a turbulent boundary layer

A technique for measuring near instantaneous concentration profiles of a fluid injected through a narrow inclined slot at the wall into a high unit Reynolds number flat plate turbulent boundary layer is discussed. The concentration profiles are determined by measuring the light intensity emitted from a fluorescent dye, premixed into the injectant flow, as the injectant convects through an excitation laser beam. The fluorescence intensity is quantified by an electronically shuttered single stage microchannel plate image intensifier coupled to a linear photodiode array. This instrumentation provided the high spatial and temporal resolution required for these boundary layer concentration profile measurements. The laser induced fluorescence technique is being used to study the diffusion of injected polymer solutions away from the near wall region of the boundary layer where these solutions are effective in reducing drag. The diffusion of slot injected water has also been examined and the present results are in excellent agreement with previous studies.     

Transition of the electronic response from molecular-like to jellium-like in cold,small sodium clusters

Absolute photoabsorption cross sections for Na _n ⁺ (2≤n≤21) were measured in the visible energy range. The cluster ions were produced in a gas aggregation source and thus have a canonical distribution of internal energy corresponding to a temperature of ～ 105 K. The spectra for n≤9 and 11 exhibit between two and six absorption lines, and are in qualitative agreement with ab inito quantum chemical calculations. For n=15 and 21, the position of the resonances can be explained as excitations of a nearly free electron gas in a spheroidal container. An evolution is thus observed from molecular-like transitions to a giant collective resonance of the electron cloud. The integrated oscillator strength is 0.95 per 3s-electron in the energy range covered for n≥4, showing that the main excitations of the valence electrons have been found.     

How Is Oxygen Incorporated into Oxides? A Comprehensive Kinetic Study of a Simple Solid‐State Reaction with SrTiO3 as a Model Material

The kinetics of stoichiometry change of an oxide--a prototype of a simple solid-state reaction and a process of substantial technological relevance--is studied and analyzed in great detail. Oxygen incorporation into strontium titanate was chosen as a model process. The complete reaction can be phenomenologically and mechanistically understood beginning with the surface reaction and ending with the transport in the perovskite. Key elements are a detailed knowledge of the defect chemistry of the perovskite as well as the application of a variety of experimental and theoretical tools, many of them evolving from this study. The importance of the reaction and transport steps for (electro)chemical applications is emphasized.