Cross section for the H+H2O abstraction reaction: experiment and theory

The absolute value of the cross section for the abstraction reaction between fast H atoms and H2O has been determined experimentally at a mean collision energy of 2.46 eV. The OH population distribution at the same mean energy has also been determined. The new measurements are compared with state-of-the-art quantum mechanical and quasiclassical scattering calculations on the most recently developed potential energy surface.     

Multichannel mueller matrix ellipsometry for simultaneous real-time measurement of bulk isotropic and surface anisotropic complex dielectric functions of semiconductors

We have applied a dual rotating-compensator multichannel ellipsometer to acquire spectra ( approximately 2.0-4.6 eV) in all 16 elements of the Mueller matrix associated with a specularly reflecting surface, in a minimum time of 0.25 s. In this initial study, such results have been collected for the (110) silicon surface at an incidence angle of approximately 70 degrees and have been used to derive spectra in the bulk isotropic dielectric function epsilon (b)= epsilon (1b)-i epsilon (2b) and the surface-induced dielectric function anisotropy Delta epsilon =Delta epsilon (1)-iDelta epsilon (2). Thus, this instrument shows promise for simultaneous real-time measurement of epsilon (b) and Delta epsilon spectra in oblique reflection during the fabrication of semiconductor structures having bulk isotropic components.     

Isobutene polymerization using a chelating diborane co-initiator

Lewis acidic diborane 1 (J. Am. Chem. Soc. 1999, 121, 3244-3245) is highly effective for both proton- and cationogen-initiated isobutene polymerization in hydrocarbon media at low temperature. Reactions of diborane 1 with cumyl chloride and cumyl methyl ether were studied by variable-temperature 1H and 19F NMR spectroscopy. At low temperatures stable ion pairs 2a and 2b are formed; at higher temperatures these ion-pairs form phenyl-1,3,3-trimethylindan (3) with concomitant release of HCl to form 1 in the case of 2a or degradation of the anion (2b). Reaction between Ph3C-Cl and diborane 1 resulted in the generation of an ion-pair 4 consisting of the Ph3C cation very weakly associated with the chelated, mu-Cl counteranion as revealed by X-ray crystallography.     

First direct structural comparison of complexes of the same metal fragment to ketenes in both C,C- and C,O-bonding modes

Using a series of Ir(I) and Rh(I) ketene complexes, conclusions about the structure and bonding of complexes of the fundamentally important ketene ligand class are reached. In a unique comparison of X-ray structures of the same metal fragment to ketenes in both the eta(2)-(C,C) and the eta(2)-(C,O) binding mode, the Ir-Cl bond distances in complexes of trans-Cl(Ir)[P(i-Pr)(3)](2) to phenylketene [4, eta(2)-(C,C)] and diphenylketene [2a, eta(2)-(C,O)] are 2.371(3) and 2.285(2) A, respectively. This would be consistent with greater trans influence of a ketene ligand bound to a metal through its C=C bond than one connected by its C=O bond. Back-bonding of Ir(I) and Rh(I) to diphenylketene was assessed using trans-Cl(M)[P(i-Pr)(3)](2)[eta(2)-(C,O)-diphenylketene] (2a and 2d). Most bond lengths and angles are identical, but slightly greater back-bonding by Ir(I) is suggested by the somewhat greater deformation of the ketene C=C=O system [C-C-O angles are 136.6(4) and 138.9(4) in the Ir and Rh cases 2a and 2d, respectively]. Syntheses of new labeled ketenes Ph(2)C=(13)C=O and Ph(2)C=C=(18)O and their Ir(I) and Rh(I) complexes are reported, along with the generation of an Ir(I) complex of PhCH=(13)C=O. The effects of isotopic substitution on infrared absorption data for ketene complexes are presented for the first time. Preliminary normal coordinate mode analysis allowed definitive assignment of absorptions ascribed to the C-O stretching frequencies of coordinated ketenes, which are near the absorptions for aromatic ring systems commonly found as substituents on ketenes. For free diphenylketene and four of its complexes and a phenylketene complex characterized by X-ray diffraction, the magnitude of the (13)C-(13)C coupling between the two ketene carbons is correlated to carbon-carbon bond distance.     

The quantitative 19F-imaging of albumin at 1.5 T: a potential in-vivo tool

19F-MR-imaging has been used to quantitate albumin concentration in a phantom at 1.5 T. The experimentally derived relationship between albumin concentration and the T1 relaxation time of a fluorinated marker, tetrafluorosuccinic acid (TFSA) was used to calculate the albumin concentration from a quantitative 19F T1 map acquired using a gradient echo sequence. There was close correlation between calculated and actual BSA concentrations (r = 0.99, SE = 0.15). The potentially interfering effect of paramagnetic species on T1 relaxation times was also investigated. Relaxivity data show that albumin concentration measurements should be performed prior to any contrast agent administration.     

A mapping approach for handling sloping interfaces

A mapping approach for handling sloping interfaces in parabolic equation solutions is developed and tested. At each range, the medium is rigidly translated vertically so that a sloping interface becomes horizontal. To simplify the approach, the slope is assumed to be small and the extra terms that arise in the wave equation under the mapping are neglected. The effects of these terms can be approximately accounted for by applying a leading-order correction to the phase. The mapping introduces variations in topography, which are relatively easy to handle for the case of a pressure-release boundary condition. The accuracy of the approach is demonstrated for problems involving fluid sediments. The approach should also be accurate for problems involving elastic sediments and should be useful for solving three-dimensional problems involving variable topography.     

An energy-conserving spectral solution

An energy-conserving spectral solution is derived and tested. A range-dependent medium is approximated by a sequence of range-independent regions. In each region, the acoustic field is represented in terms of the horizontal wave-number spectrum. A condition corresponding to energy conservation is derived for the vertical interfaces between regions. The accuracy of the approach is demonstrated for problems involving sloping ocean bottoms. The energy-conserving spectral solution is less efficient than the energy-conserving parabolic equation solution, but might be suitable for generalization to problems involving elastic bottoms.     

Is the intrinsic thermoelectric power of carbon nanotubes positive?

The thermoelectric power (TEP) of single-walled carbon nanotubes (SWNTs) is extremely sensitive to gas exposure history. Samples exposed to air or oxygen have an always positive TEP, suggestive of holelike carriers. However, at fixed temperature the TEP crosses zero and becomes progressively more negative as the SWNTs are stripped of oxygen. The time constant for oxygen adsorption/desorption is strongly temperature dependent and ranges from seconds to many days, leading to apparently "variable" TEP for a given sample at a given temperature. The saturated TEP can be accounted for within a model of strong oxygen doping of the semiconducting nanotubes.     

Progress in direct-drive inertial confinement fusion research at the laboratory for laser energetics

Direct-drive inertial confinement fusion (ICF) is expected to demonstrate high gain on the National Ignition Facility (NIF) in the next decade and is a leading candidate for inertial fusion energy production. The demonstration of high areal densities in hydrodynamically scaled cryogenic DT or D₂ implosions with neutron yields that are a significant fraction of the “clean” 1-D predictions will validate the ignition-equivalent direct-drive target performance on the OMEGA laser at the Laboratory for Laser Energetics (LLE). This paper highlights the recent experimental and theoretical progress leading toward achieving this validation in the next few years. The NIF will initially be configured for X-ray drive and with no beams placed at the target equator to provide a symmetric irradiation of a direct-drive capsule. LLE is developing the “polar-direct-drive” (PDD) approach that repoints beams toward the target equator. Initial 2-D simulations have shown ignition. A unique “Saturn-like” plastic ring around the equator refracts the laser light incident near the equator toward the target, improving the drive uniformity. LLE is currently constructing the multibeam, 2.6-kJ/beam, petawatt laser system OMEGA EP. Integrated fast-ignition experiments, combining the OMEGA EP and OMEGA Laser Systems, will begin in FY08.