Structure of 72,74Se at high spin

Lifetimes of high spin states up to { }=22⁺ in the yrast positive parity bands have been measured to investigate the shape evolution with increasing spin in ^{72, 74}Se. The Q _t values derived from these measurements indicate that prolate shape stabilizes for ⁷²Se, while a triaxial shape develops for ⁷⁴Se at higher spins. Comparison of the observed trend in Q _t with spin for ^{72, 74}Se with that of the corresponding kryptones isotones emphasizes the stability provided by N=38 prolate shell gap even at high rotational frequency.     

An advanced LIF-PLV system for analysing the hydrodynamics in a laboratory bubble column at higher void fractions

Bubble columns are widely used in the chemical industry and biotechnology. Flow and turbulence in such an apparatus are induced by the bubble rise, and the bubble behaviour is strongly affected by swarm effects (i.e. the interaction between bubbles). For analysing the bubble swarm behaviour and simultaneously evaluating the flow structure and bubble-induced turbulence, a bubble column of 140 mm diameter and a height of 650 mm or 1,400 mm (initial water level) were considered. The bubble column was aerated with relatively fine bubbles having a mean size between about 0.5 and 4.0 mm. The gas hold-up was varied in the range between 0.5 and 19%. A two-phase pulsed-light velocimetry (PLV) system was developed to evaluate instantaneous flow fields of both rising bubbles and the continuous phase. The measurement of the liquid velocities in the bubble swarm was achieved by adding fluorescing seed particles. Images of bubbles and fluorescing tracer particles were acquired by two CCD cameras. Hence, the images from tracers and bubbles were easily separated by optical interference filters with a bandwidth corresponding to the emitting wavelength of the fluorescing tracer particles and the wavelength of the applied Nd-YAG pulsed laser, respectively. To improve the phase separation of the system, the CCD cameras were additionally placed in a non-perpendicular arrangement with respect to the light sheet. The acquired images were evaluated with the minimum-quadratic-difference algorithm. The potential of this technique for the analysis of bubbly flows with higher void fraction was explored. In order to obtain averaged velocity maps of bubble and fluid within the entire column, about 1,000 image pairs were recorded and evaluated for each phase. In addition, turbulence intensities of the fluid were deduced from the measurements. The turbulence properties were used to characterise bubble-induced turbulence for various bubble mean diameters and gas hold-ups. Moreover, the determination of the average bubble slip velocity within the bubble swarm was possible.     

Experimental and numerical studies of shock wave focusing in water

The focusing of plane shock waves and spherical blast waves in water by parabolic and ellipsoidal reflectors is studied experimentally and numerically. The numerical computations are performed by a second order method based on an extension of Godunov's method, which is called piecewise-linear method. Tests of this method and a comparison with pressure measurements show a strong dependence of the maximum pressure attained in the focal region on the mesh size. Outside this focal region, however, good agreement between the pressure measurements and the result of the numerical computation is found. Furthermore it is shown by numerical computation, that non-linear effects in the focusing process may be partly avoided by an optimized reflector contour which depends on the strength of the incident shock wave. This modification provides that the maximum pressure is attained at the geometric focus and not at a location between reflector surface and geometrical focus.     

Negative ions of nitroethane and its clusters

Valence and dipole-bound negative ions of the nitroethane (NE) molecule and its clusters are studied using photoelectron spectroscopy (PES), Rydberg electron transfer (RET) techniques, and ab initio methods. Valence adiabatic electron affinities (EA(a)s) of NE, C(2)H(5)NO(2), and its clusters, (C(2)H(5)NO(2))(n), n=2-5, are estimated using vibrationally unresolved PES to be 0.3+/-0.2 eV (n=1), 0.9+/-0.2 eV (n=2), 1.5+/-0.2 eV (n=3), 1.9+/-0.2 eV (n=4), and 2.1+/-0.2 eV (n=5). These energies were then used to determine stepwise anion-neutral solvation energies and compared with previous literature values. Vertical detachment energies for (C(2)H(5)NO(2))(n)(-) were also measured to be 0.92+/-0.10 eV (n=1), 1.63+/-0.10 eV (n=2), 2.04+/-0.10 eV (n=3), and 2.3+/-0.1 eV (n=4). RET experiments show that Rydberg electrons can be attached to NE both as dipole-bound and valence bound anion states. The results are similar to those found for nitromethane (NM), where it was argued that the diffuse dipole state act as a "doorway state" to the more tightly bound valence anion. Using previous models for relating the maximum in the RET dependence of the Rydberg effective principle number n(max)(*), the dipole-bound electron affinity is predicted to be approximately 25 meV. However, a close examination of the RET cross section data for NE and a re-examination of such data for NM finds a much broader dependence on n(*) than is seen for RET in conventional dipole bound states and, more importantly, a pronounced [l] dependence is found in n(max)(*) (n(max)(*) increases with [l]). Ab initio calculations agree well with the experimental results apart from the vertical electron affinity value associated with the dipole bound state which is predicted to be 8 meV. Moreover, the calculations help to visualize the dramatic difference in the distributions of the excess electron for dipole-bound and valence states, and suggest that NE clusters form only anions where the excess electron localizes on a single monomer.     

Small gas-phase dianions of Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-)

We have searched for new species of small oxygen-containing gas-phase dianions produced in a secondary ion mass spectrometer by Cs+ ion bombardment of solid samples with simultaneous exposure of their surfaces to O2 gas. The targets were a pure zinc metal foil, a copper-contaminated zinc-based coin, two silicon-germanium samples (Si(1-x)Ge(x)(with x= 6.5% or 27%)) and a piece of titanium metal. The novel dianions Zn3O(4)(2-), Zn4O(5)(2-), CuZn2O(4)(2-), Si2GeO(6)(2-), Ti2O(5)(2-) and Ti3O(7)(2-) have been observed at half-integer m/z values in the negative ion mass spectra. The heptamer dianions Zn3O(4)(2-) and Ti2O(5)(2-) have been unambiguously identified by their isotopic abundances. Their flight times through the mass spectrometer are approximately 20 micros and approximately 17 micros, respectively. The geometrical structures of the two heptamer dianions Ti2O(5)(2-), and Zn3O(4)(2-) are investigated using ab initio methods, and the identified isomers are compared to those of the novel Ge2O(5)(2-) and the known Si2O(5)(2-) and Be3O(4)(2-) dianions.     

Synthesis of N‐alkoxybenzimidoyl azides and their reactions in electrophilic media

A new general route to N‐alkoxybenzimidoyl azides [ArC(N₃)=NOR] from a reaction of N‐alkoxybenzimidoyl bromide [ArC(Br)=NOR] with sodium azide in DMSO is described. These reactions result in the Z‐geometric configuration. These compounds show a moderate degree of thermal stability as assessed by differential scanning calorimetry, and lack reactivity in traditional 1,3‐dipolar cycloaddition ‘click’ reactions. Upon exposure to electrophilic compounds (trifluoroacetic acid or acetyl chloride), these azide compounds can react by two pathways: a Schmidt‐type rearrangement to form an N‐alkoxyurea or an isomerization–cyclization reaction pathway to form an N‐alkoxytetrazole. The route of the reaction has no dependence on solvent polarity and appears to depend upon the electrophile (H⁺ vs. CH₃CO⁺): reaction of the azide with trifluoroacetic acid results predominantly in the urea; reaction with acetyl chloride results solely in the tetrazole. Calculations indicate that the urea product is thermodynamically favored over the tetrazole product. They also indicate that both reaction conditions result in an equilibration between the starting azide and the tetrazole with the tetrazole being the major component in this equilibrium mixture. The fact that the azide also undergoes a Schmidt‐type rearrangement to form an N‐alkoxyurea when treated with trifluoroacetic acid appears to indicate that the barrier for aromatic ring migration is lower in the protonated azide produced on reaction with trifluoroacetic acid than in the acetylated azide produced on reaction with acetyl chloride. Copyright © 2009 John Wiley & Sons, Ltd.