Influence of the H/F replacement on the homoaromaticity of homotropylium ion: a GIAO/DFT theoretical study

The problem of homoaromaticity in mono-, di- and polyfluorinated- homotropylium cations is addressed by the B3LYP/6-311++G** DFT method. The energetic, structural and magnetic criteria are used for this purpose. They convincingly show that the ground state equilibrium species are aromatic, or in other words that the homoaromaticity is preserved by the (poly)fluorination. In contrast, a considerable decrease in the aromatic stabilization is observed in the transition structures (TS). According to the NICS(0) index, they vary form strongly antiaromatic, via weakly and non-aromatic to slightly aromatic transition states. However, the hierarchy of the aromaticity in fluorinated homotropylium ions predicted by NICS(0) is completely unrelated to that obtained by using the energy criterion assuming a kinetic definition of aromaticity. On the other hand the latter is closely related to geometric parameters of the equilibrium and transition structures.     

Simulation of single‐ and two‐phase flows on sliding unstructured meshes using finite volume method

The paper presents an efficient finite volume method for unstructured grids with rotating sliding parts composed of arbitrary polyhedral elements for both single‐ and two‐phase flows. Mathematical model used in computations is based on the ensemble averaged conservation equations. These equations are solved for each phase and in case of single‐phase flow reduce to the transient Reynolds‐averaged Navier–Stokes (TRANS) equations. Transient flow induced by rotating impellers is thus resolved in time. The use of unstructured grids allows an easy and flexible meshing for the entire flow domain. Polyhedral cell volumes are created on the arbitrary mesh interface placed between rotating and static parts. Cells within the rotating parts move each time step and the new faces are created on the arbitrary interfaces only, while the rest of the domain remain ‘topologically’ unchanged. Implicit discretization scheme allows a wide range of time‐step sizes, which further reduce the computational effort. Special attention is given to the interpolation practices used for the reconstruction of the face quantities. Mass fluxes are recalculated at the beginning of each time step by using an interpolation scheme, which enhances the coupling between the pressure and velocity fields. The model has been implemented into the commercially available CFD code AVL SWIFT (AVL AST, SWIFT Manual 3.1, AVL List GmbH, Graz, Austria, 2002). Single‐phase flow in a mixing vessel stirred by a six‐bladed Rushton‐type turbine and two‐phase flow in aerated stirred vessel with the four‐blade Rushton impeller are simulated. The results are compared with the available experimental data, and good agreement is observed. The proposed algorithm is proved to be both stable and accurate for single‐phase as well as for the two‐phase flows calculations. Copyright 2004 John Wiley & Sons, Ltd.     

Time resolved spectroscopic NMR imaging using hyperpolarized Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized ¹²⁹Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

Production of heavy nuclei in the interaction of <Superscript>7</Superscript>Li ions with copper nuclei at an energy of 35 MeV per nucleon

The absolute values of the cross sections for the production of target fragments in the interaction of copper with ⁷Li ions at an energy of 35 MeV per nucleon were measured. The measurements were performed by recording the yields of radioactive nuclear residues with the aid of a semiconductor detector from ultrapure germanium. The charge and isobaric distributions in the mass-number range 22–69 amu were used to deduce the mass yield of reaction products and to calculate the total interaction cross section. The results are presented that were derived from a comparison with data obtained for ¹²C + Cu reactions and with estimates based on theoretical models.     

Searches for single-spin asymmetry in the inclusive production of neutral pions in the central region at a proton beam energy of 70 GeV

Results are presented that were obtained by measuring single-spin asymmetry in the inclusive production of neutral pions in the reaction p+p ↑→ π ⁰+X at x _F≈0. A beam of 70-GeV protons was extracted directly from the vacuum chamber of the accelerator by means of a bent single crystal. For transverse momenta in the range 1.0<p _T<3.0 GeV/c, the single-spin asymmetry independently measured by two detectors is zero within the errors. This result is in agreement with Fermilab data obtained at 200 GeV, but it is at odds with CERN data measured at 24 GeV.     

High-efficiency erbium ion luminescence in silicon nanocrystal systems

The photoluminescence spectra and kinetics of both erbium-doped and undoped multilayer structures of quasi-ordered silicon nanocrystals in a silicon dioxide matrix were studied. It was shown that the optical excitation energy of silicon nanocrystals 2–3 nm in size can be practically completely transferred to Er³⁺ ions in the oxide surrounding the nanocrystals, with its subsequent radiation at 1.5 μm. Possible reasons for the high excitation efficiency of the Er³⁺ ions are discussed, and the conclusion is drawn that the F?rster mechanism is dominant in the energy transfer processes occurring in these structures. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 1, 2004, pp. 105–109. Original Russian Text Copyright ? 2004 by Kashkarov, Kamenev, Lisachenko, Shalygina, Timoshenko, Schmidt, Heitmann, Zacharias.     

Ultrashort electron beam and volume high-current discharge in air under the atmospheric pressure

Conditions are studied under which an electron beam and a volume discharge with a subnanosecond rise time of a voltage pulse are produced in air under atmospheric pressure. It is shown that the electron beam appears in a gas-filled diode at the front of the voltage pulse in ∼0.5 ns, has a half-intensity duration of ≤0.4 ns and an average electron energy of ∼0.6 of the voltage across the gas-filled diode, and terminates when the voltage across the gap reaches its maximum value. The electron beam with an average electron energy of 60 to 80 keV and a current amplitude of ≥70 A is obtained. It is assumed that the electron beam is formed from electrons produced in the gap due to gas ionization by fast electrons when the intensity of the field between the front of the expanding plasma cloud and the anode reaches its critical value. A nanosecond volume discharge with a specific power input of ≥400 MW/cm³, a density of the discharge current at the anode of up to 3 kA/cm², and specific energy deposition of ∼1 J/cm³ over 3 to 5 ns is created.     

Method for calculating the field of an opaque source and the field scattered by an inhomogeneous inclusion in a planar layered waveguide

Acoustical Physics - A method for calculating the resulting field of an opaque radiator and the field scattered by an inhomogeneous inclusion in a planar layered waveguide is described. The...