Photoinduced electron transfer variables: rigidity or orientation?

The relatives photoreactives of bridged-ring systems 1, 3, 5-X and 6-X (X ≡ Cl or Br) have been studied at 254 nm in acetic acid. The formation of photosolvolysis product was rationalized in terms of photoinduced intramolecular electron transfer (ET) processes. The relative ease of ET in these donor—bridge—acceptor model system was analyzed in terms of known ET variables including free-energy changes, orientation effects and ridigity effects. The observed relative photoreactivities agreed better with the calculated free-energy changes when relative rigidities of the electron acceptor termini were evaluated. In general, the more rigid system were more photoreactive.     

Pressure-induced dislocation amorphization of crystals

In terms of the isotropic elastic crystal model, it is shown that the formation of planar layers consisting of edge dislocation pileups is advantageous in energy if the shear modulus of the crystal is far lower than the bulk modulus. As pressure rises, the dislocation radius decreases, which can destroy the crystal structure.     

Resonance ionization spectroscopy for trace analysis and fundamental research

Resonance ionization spectroscopy (RIS) and its combination with mass spectrometry (RIMS) have grown to become powerful techniques, which offer high sensitivity as well as elemental and isotopic selectivity. The principles of RIS and RIMS are introduced; they primarily concern the analysis of the optical spectra for the choice of efficient excitation schemes and the suitable design of the experimental apparatus. Recent applications span from studies of short-lived isotopes at on-line mass separators to a wide variety of trace analysis applications for radioactive isotopes, which can range from measurements of solar neutrino flux to environmental assessment.On leave from Pacific Northwest Laboratory, Richland, USA     

Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Analysis of the structure of an amorphous sediment obtained upon decomposition of potassium oxofluroniobate in water

An amorphous sediment was prepared by the decomposition of potassium oxofluoroniobate K_{2 ? x} Nb₄O₃(O, F)₃F in water. For this sediment, the atomic radial distribution function was analyzed with the use of a fragment model, which allows one to interpret expanded coordination spheres as being formed by first several strongest diffusion maxima. These spheres carry the most reliable information on the structure. It is shown that the amorphous sediment consists of the randomly packed Nb(O,F)₆-octahedra with interatomic distances close to those observed in the ordered region in the N-Nb₂O₅ structure. During decomposition in water, the initial K_{2 ? x} Nb₄O₃(O, F)₃F phase loses KF-layers, whereas Nb₆ clusters with metal bonds are destroyed.