Surface layer self diffusion in icosahedral Al-Pd-Mn quasicrystals

The self diffusion of Mn and Pd in a single grain icosahedral Al_69.9Pd_20.5Mn_9.6 quasicrystal has been determined by low energy ion scattering (LEIS). The diffusion was determined by depositing different elements (Pd, Mn) on the surface and measuring the rate of change in surface composition as a function of temperature by LEIS. The surface composition was monitored over the temperature range of 355-575 K for Mn and 440-745 K for Pd and compared to model calculations to allow the activation energy for diffusion to be determined. Activation energies of 0.20 ± 0.01 eV for Mn and 0.64 ± 0.03 eV for Pd have then been measured for self diffusion in i-Al-Pd-Mn, respectively. No deviation from Arrhenius behavior was detected in the temperature range covered by the present experiments. From the low values of activation energy we propose that this range of diffusion is phason related, reflecting the specific nature of the icosahedral structure.     

Children's Books Reviewed

Maps and Globes Jack Knowlton Hurricane Watch Franklyn M. Branley Sunshine Makes the Seasons Franklyn M. Branley Heart Disease America's No. 1 Killer Dr. Alvin and Virginia B. Silverstein Cuts, Breaks, Bruises and Burns Joanna Cole Auks, Rocks, and the Odd Dinosaur Inside Stories from the Smithsonian Institute by Peggy Thomson The Secret Life of Cosmetics: A Science Experiment Book Vicki Cobb A Children's Zoo Tana Hoban Milk Donald Carrick Wallaby Creek Joyce Powzyk Being a Twin, Having a Twin Maxine Rosenberg     

Crystal and molecular structure of tetraiodo (1,8-di-2-pyridyl-3,6-dithiaoctane-N,S,S′,N′)dimercury(II)

Summary The X-ray crystal structure of the title compound, [Hg₂(C₁₆H₂₀N₂S₂)I₄], has been determined. The crystals are monoclinic (space groupP2₁/c), with cell dimensionsa=15.016(2),b=6.201(3),c=15.273(2) Å,=115.18(1)°;V _o =1287.0(7) ų,M _r =1213.266,Z=4,D _x =6.26mg m^–3, MoK radiation (graphite crystal monochromator, ),(MoK)=336 cm^–1,F(000)=4272, andT=290°K. The final conventionalR factor=0.054, andR _w =0.062 for 2799 observed reflections. The structure was solved by Patterson and Fourier methods and refined by block-diagonal least-squares methods. The coordination around the mercury atoms is approximately tetrahedral, although with considerable distortion, with two iodine atoms and the N and S atoms of one-half of the ligand molecule.     

A comprehensive and compact n-heptane oxidation model derived using chemical lumping

A detailed reaction mechanism for n-heptane oxidation has been compiled and subsequently simplified. The model is based on a kinetic model for C1-C4 fuel oxidation of Hoyermann et al. [Phys. Chem. Chem. Phys., 2004, 6, 3824] and a detailed mechanism for n-heptane oxidation developed by Curran et al. [Combust. Flame, 1998, 114, 149]. The generated mechanism is kept compact by limiting the application of the low temperature oxidation pathways to the fuel molecule. The first reaction steps and the complex low temperature paths in the oxidation process have been simplified and reorganized by linear chemical lumping. The reported procedure allows a decrease in number of species and reactions with only a minor loss of model accuracy. The simplified model is of very compact size and gives an advantageous starting point for further model reduction. By this chemically lumped general mechanism without further adjustments the large set of experimental data for the high and low temperature oxidation (ignition delay times, species concentration profiles, heat release and engine pressure profiles, flame speeds and flame structure data) for conditions ranging from very low to high temperatures (550-2300 K), very lean to extremely fuel rich (0.22 < phi < 3) mixtures and pressures between 1 and 42 bar is consistently described providing a basis for reliable predictions for future applications, (i) building reaction mechanisms for similar but chemically more complex fuels (e.g. iso-octane, n-decane,...) and (ii) calculating complex flow fields ("fluid dynamics") after further simplification with advanced reduction tools.     

C-24 stereochemistry of marine sterols: (22E)-24-(isopropenyl)-22-dehydrocholesterol and 24-isopropenylcholesterol

The C-24 configuration of (22E,24xi)-24-isopropenyl-22-dehydrocholesterol (1), which was recently isolated from the Colombian Caribbean sponge, Topsentia ophiraphidites, was investigated. Synthesis of the stereodefined (24R)- and (24S)-(22E)-24-isopropenyl-22-dehydrocholesterols (1a, 1b) followed by (1)H- and (13)C-NMR data comparison of these sterols established the (24R)-configuration of 1. In addition, (24R)- and (24S)-24-isopropenylcholesterols (2a and 2b) were also synthesized and their NMR data are provided. The C-24 configurations of the samples of 24-isopropenylcholesterol reported previously are discussed.     

Volumetric, Electric, and Magnetic Properties of Thioxanthen-9-one in Aprotic Solvents as Revealed by High-Precision Densitometry, High-Accuracy Refractometry and Magnetic Susceptibility Measurements and by DFT Calculations

High-precision densitometry measurements of solutions of thioxanten-9-one (TX) in 1,4-dioxane, DMSO, toluene, and benzene have been obtained at 293.15, 303.15, 313.15, 323.15, 333.15, and 343.15K. The partial molar volumes of TX ( ) and the corresponding values at infinite dilution ( ) were determined. The partial molar expansibility ( ) of TX at infinite dilution in each solvent is temperature independent. Dynamic electronic polarizabilities of TX in each aprotic solvent were determined by the Singer–Garito approach. These values are in excellent concordance with the theoretical value for TX of 2.611×10⁻²³cm³ estimated here using DFT/B3LYP/6-311++G(d,p). The partial molar volumes of TX at infinite dilution were calculated and interpreted in terms of the Scale Particle Theory (SPT). The solvent influence on the partial molar volume of TX was found to be due mainly to cavity formation and intermolecular dispersion forces.     

High spatiotemporal resolution in multifocal processing with femtosecond laser pulses

We report spatial and temporal dispersion compensation for fan-out of femtosecond pulses with a low-frequency diffraction grating by means of a hybrid diffractive-refractive lens triplet. In this way, we achieve a multifocal light structure with nearly diffraction-limited light spots even for 20 fs pulse duration. The spatial chromatic compensation, which drastically reduces the lateral walk-off of the various spectral components, also allows us to improve the available bandwidth at the dispersion-compensated diffraction orders. In fact, the temporal width of the output pulse is essentially limited by the group-delay dispersion term, which is shown to be small. The high spatiotemporal resolution provided by our proposal permits parallel multifocal processing of materials with femtosecond pulses.