Generators for categories of compact irreducible semigroups

For a compact totally ordered space X, K. H. Hofmann and P. S. Mostert constructed a topological semigroup Irr (X)₀ such that every compact irreducible semigroup with idempotents X is a surmorphic image of Irr (X)₀ [2]. J. H. Carruth and M. Mislove pointed out that Irr (X)₀ was in general not a compact semigroup. In this paper a compact connected hormos will be constructed which contains Irr (X)₀ as a dense subsemigroup and for which every compact irreducible semigroup with idempotents X is a surmorphic image. This leads to a new proof of the existence of generators for the category of compact irreducible semigroups with idempotents X. It will then be shown that Irr (X)₀ contains generators for the category.     

Endor frequencies of randomly oriented triplets by electron spin echo spectroscopy

ENDOR frequencies of randomly oriented triplets have been measured from the fast Fourier transform of electron spin echo envelope modulation. Important experimental conditions are low temperatures, high microwave power and long phase memory time in a proper form of solvent. The technique is exemplified by using diphenylmethylenes in rigid glasses, polycrystalline forms and single crystals of benzophenones.     

Electron spin echo envelope modulation of trapped radicals in disordered systems: nitrogen modulation from isotopically substituted chlorophyll a cations

The electron spin echo envelope modulation of the chlorophyll a radical cation has been examined for radicals containing ¹⁴N and ¹⁵N. The modulation is found to be due primarily to the nitrogen nuclei in the heterocycle and the nuclear quadrupole interaction plays a large part in determining the modulation from ¹⁴N. The modulation from ¹⁵N allows limits to be set on the isotropic and anisotropic hyperfine interactions.     

Asymptotic series and Stieltjes continued fractions for a gamma function ratio

An analysis is given for the expansion (60 terms) of a gamma function ratio discussed by Stieltjes and others. A Stieltjes continued fraction is derived, affording lower and upper bound (but lacking a rigorous proof), along with continued fraction for the odd and even series.     

Magnetic alignment in nominally non-magnetic hexagonal metal hydrides: NMR

Powders of three hexagonal metal-hydrides or -deuterides are found to align in 4.4–8.3 T magnetic fields used for NMR. The field-alignment is unexpected, since all three systems have very small susceptibilities, as demonstrated by sharp NMR lines. The extent of alignment runs from nearly complete to barely detectable in ZrBe₂(H,D)_x, LuD₃, and YD₃, respectively. The preferred alignment direction in ZrBe₂(H,D)_x is with the crystallites’ c-axis perpendicular to B, while the c-axis and B tend to be parallel in LuD₃ and YD₃. The susceptibilities χ_|| and χ are determined from bulk magnetization measurements in aligned ZrBe₂H_1.4 powder. The alignment must be considered for proper analysis of NMR spectra in these and related materials.     

Superior electromechanical performance over PZT, in lead zinc niobate (PZN)–lead zirconium titanate (PZT) thin films

Strongly oriented thin films of lead zinc niobate (PZN)–lead zirconium titanate (PZT) with (La,Sr)CoO₃ lower electrodes were grown on MgO {001} substrates by pulsed laser deposition. The films were perovskite-dominated with strong in-plane and out-of-plane orientations. Room-temperature functional characterisation indicated that the films were ferroelectric, with dielectric constant ∼550 and loss tangent ∼0.08 at 1 kHz. The crystallographic strain, as a function of applied dc field, was monitored by in situ X-ray diffraction. The maximum electric-field-induced crystallographic strain (∼0.22%) was comparable to that observed in bulk, but at significantly greater field (∼150 kV cm^-1). The effective d₃₃ value obtained from the crystallographic strain data was around 150 pm V^-1, which is high for ferroelectric thin films 400 nm in thickness. The local polarisation-switching properties of the films were investigated using a piezo-response atomic force microscope. Domain maps for a 5×5 μm² region of material were recorded as a function of dc bias, and confirmed the ferroelectric switching behaviour. PACS 81.05.Je; 81.40.Vw; 68.37.Lp     

Influence of the secondary functionality on the radical‐vinyl chemistry of highly reactive monoacrylates

The impact of secondary functionalities on the radical‐vinyl chemistry of monoacrylates characterized by secondary functionalities that dramatically enhance their polymerization rate was elucidated utilizing experimental and computational techniques. Firstly, bulk interactions affecting the acrylate reactivity towards photopolymerization were removed by polymerizing at 5 wt % monomer in 1,4‐dioxane. Following deconvolution of bulk interactions impacting reactivity towards photopolymerization, a linear correlation between average polymerization rates and Michael addition reaction rate constants was observed on a logarithmic scale. This result indicates that the presence of the secondary functionality intramolecularly alters the monomer chemistry in a manner which impacts both of these distinct reaction types in a similar manner. These monomers exhibited reduced activation energies in both Michael addition and photopolymerization reactions as compared to hexyl acrylate. Reduction up to 20 ± 8 kJ mole^?1was observed for Michael addition reactions and 12 ± 1 kJ mole^?1 for photopolymerization reactions, thereby explaining the higher reactivity of the acrylates characterized by the secondary functionalities. Cyclic voltammetry experiments conducted to investigate the nature of the acrylic double bonds indicated that the rapidly polymerizing acrylates are more readily reduced as compared to traditional acrylates. Further, a distinct monotonic correlation of the irreversible cathodic peak potentials of the (meth)acrylates to photopolymerization and Michael addition reactivity was observed. The computationally estimated acrylic LUMO energies characterized by the secondary functionalities (?2.3 eV to ?2.7 eV) were also found to be lower relative to hexyl acrylate (?2.2 eV). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4859–4870, 2009     

High‐temperature shock tube study of the reactions CH3 + OH → products and CH3OH + Ar → products

The reaction between methyl and hydroxyl radicals has been studied in reflected shock wave experiments using narrow‐linewidth OH laser absorption. OH radicals were generated by the rapid thermal decomposition of tert‐butyl hydroperoxide. Two different species were used as CH₃ radical precursors, azomethane and methyl iodide. The overall rate coefficient of the CH₃ + OH reaction was determined in the temperature range 1081–1426 K under conditions of chemical isolation. The experimental data are in good agreement with a recent theoretical study of the reaction. The decomposition of methanol to methyl and OH radicals was also investigated behind reflected shock waves. The current measurements are in good agreement with a recent experimental study and a master equation simulation. © 2008 Wiley Periodicals, Inc. 40: 488–495, 2008