Role of hyperconjugation in determining carbon-oxygen bond dissociation enthalpies in alkylperoxyl radicals

[reaction: see text] Theoretical calculations of carbon-oxygen bond dissociation enthalpies in substituted methylperoxyl radicals (YCH(2)OO*) reveal that bond strengths are not governed solely by the stability of YCH2* radicals but are largely affected by hyperconjugation when Y is electron-donating or conjugating. In many cases, this hyperconjugative effect is greater than stabilization of the methyl radical by Y. All electron-withdrawing Y exert small destabilizing effects via inductive withdrawal of electrons from the polarized C-OO* bond.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Dependence of pulser driving responses on electrical and motional characteristics of NDE ultrasonic probes

Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results.     

An optical study of phase transitions of poly (ethylene terephthalate-co-p-hydroxybenzoic acid) liquid crystal

The copolyester containing 40 mol % ethylene terephthalate (PET) and 60 mol % p-hydroxybenzoate (HB) units has been reported by several investigators to be biphasic in the solid and the liquid states. The reported thermal transitions in the two phases, however, are in part contradictory, perhaps partly due to different polymerization conditions. The present work is a study of the transitions in each of the two phases of this copolyester by polarized light microscopy and by light transmission measurements. By light transmission measurements, the two phases were found to have two different glass transition temperatures for the onset of segmental motion, consistent with two assignable temperatures (T.). Cold crystallization and melting in each of the two different phases was also detected. The results help clarify the nature of transitions and agree with the results of dynamic mechanical analysis on the same thermotropic liquid crystalline copolyester.     

A new approximation method for scattering by long finite arrays

The scattering of water waves by a long array of evenly spaced,rigid, vertical circular cylinders is analysed under the usualassumptions of linear theory. These assumptions permit the reductionof the problem to that of solving the Helmholtz equation intwo dimensions, with appropriate circular boundaries. Our primarygoal is to show how solutions obtained for semi-infinite arrayscan be combined to provide accurate and numerically efficientsolutions to problems involving long, but finite, arrays. Theparticular diffraction problem considered here has been chosenboth for its theoretical interest and for its applicability.The design of offshore structures supported by cylindrical columnsis commonplace and understanding how the multiple interactionsbetween the waves and the supports affect the field is clearlyimportant. The theoretical interest comes from the fact that,for wavelengths greater than twice the geometric periodicity,the associated infinite array can support Rayleigh–Blochsurface waves that propagate along the array without attenuation.For a long finite array, we expect to see these surface wavestravelling back and forth along the array and interacting withthe ends. For particular sets of parameters, near-trapping haspreviously been observed and we provide a quantitative explanationof this phenomenon based on the excitation and reflection ofsurface waves by the ends of the finite array.     

Eisenuntersuchungen

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