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Notes: The formation and decomposition of formate species on the clean and on potassium-modified Ru(001) surfaces have been investigated with time-resolved vibrational spectroscopy and thermal desorption mass spectrometry (TDMS). Utilizing Fourier transform-infrared reflection absorption spectroscopy (FT-IRAS) we have characterized chemisorbed formate produced by the decomposition of formic acid on clean Ru(001), Ru(001)–((square root of)3×(square root of)3)R30° K and on a K-multilayer adsorbed on Ru(001). The vibrational spectra show that formate is adsorbed on both clean Ru(001) and Ru(001)–((square root of)3×(square root of)3)R30° K with C2v symmetry indicative of a bridged or bidentate species. There are, however, characteristic differences in the vibrational spectra, which indicate that for the Ru(001)–((square root of)3×(square root of)3)R30° K surface the formate is directly bound to potassium. The vibrational spectrum of the latter species is found to be in good agreement with that of bulk potassium formate adsorbed on Ru(001).Based on the agreement with literature data for bulk formate, we propose a bonding model for the potassium formate monolayer, which also accounts for the observed contraction of the potassium monolayer resulting from the compound formation. The thermal decomposition of the various formate overlayers has been monitored by simultaneous thermal desorption mass spectrometry and time-resolved FT-IRAS. This combination allows us to correlate the desorbing gas-phase products with the appearance and disappearance of surface intermediates. In the case of formate adsorbed on the clean Ru(001), the C–H and C–O bond cleavage reactions occur simultaneously, leading to the production of equal amounts of CO and CO2. The simultaneous observation of desorbing CO2 (TDMS) and of adsorbed CO (IR) confirms earlier work, which postulated a mechanism involving a coupling of the C–H and C–O bond cleavage reaction channels of two neighboring formates. The presence of potassium changes dramatically the reaction pathway of the formate as it suppresses the C–H bond cleavage channel, leaving CO and OH as the main decomposition products. Compound formation with potassium also leads to thermal stabilization of the formate in comparison to formate adsorbed on the clean surface. However, formate adsorbed on the potassium-modified ruthenium substrate is found to be thermally less stable than formate adsorbed on clean Ru(001).

Notes: The kinetics of decomposition of formic acid on Ru(001) have been investigated with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH at both 130 and 305 K. Formic acid chemisorbs dissociatively on the perfect (001) surface via O–H bond cleavage to form a formate and a hydrogen adatom, and at defect (step) sites on the surface via C–O bond cleavage to form CO, a hydrogen adatom and a hydroxyl. The saturation fractional coverage of the dissociatively chemisorbed formic acid is approximately 0.33 following adsorption at 130 K, and approximately 0.49 following adsorption at 305 K. Thermal desorption spectra of CO2 are a direct probe of the kinetics of C–H bond cleavage of the formate and are characterized by a kinetic isotope effect (C–H vs C–D bond cleavage), a progressively narrowing peak width, and an upward shift in peak temperature with increasing surface coverage of the formate.The latter indicates an increasing apparent activation energy for the C–H bond cleavage reaction with increasing formate coverage, which results in self-accelerating decomposition kinetics that cause the observed sharp peak in the production of CO2. Although the activation energy for the C–H bond cleavage reaction varies strongly with the formate coverage, the relative yields of CO2 and CO are independent of the formate coverage and are in a ratio of 1:1. This observation, together with the observation that the formation of HDO and D2O, which results from C–O bond cleavage of the formate, appears at approximately the same temperature as that of CO2 formation following saturation adsorption of DCOOH at both 130 and 305 K, prove that cleavage of the C–D and C–O bonds of the formate are not two independent reaction pathways.A novel mechanism for the reaction is postulated which involves the hydrogen from the C–H bond cleavage reaction in one formate (producing carbon dioxide) reacting with an adjacent formate to form a hydroxyl and formyl. The latter react to form the other observed products: carbon monoxide, and a mixture of water and molecular hydrogen, with some chemisorbed oxygen remaining on the surface. The increase in the activation energy for decomposition of the formate with increasing formate coverage is due to the fact that a chemisorbed formate is stabilized by the presence of another nearby formate.

Notes: An amplitude method is described for determining the partial and total widths and the energies of resonances in multichannel processes in which resonance states may decay into many channels. The method is tested by application to a model problem and by a study of the predissociation of the C 3Πg Rydberg state of O2.

Notes: A numerically exact spectral method for solving the time-dependent Schrödinger equation in spherical coordinates is described. The angular dependence of the wave function is represented on a two-dimensional grid of evenly spaced points. The fast Fourier transform algorithm is used to transform between the angle space representation of the wave function and its conjugate representation in momentum space. The time propagation of the wave function is evaluated using an expansion of the time evolution operator as a series of Chebyshev polynomials. Calculations performed for a model system representing H2 scattering from a rectangular corrugated surface yield transition probabilities that are in excellent agreement with those obtained using the close-coupling wave packet (CCWP) method. However, the new method is found to require substantially more computation time than the CCWP method because of the large number of grid points needed to represent the angular dependence of the wave function and the variation in the number of terms required in the Chebyshev representation of the time evolution operator.

Notes: The close coupling wave packet (CCWP) method is formulated in a body-fixed representation for atom–rigid rotor inelastic scattering. For total J〉jmax the computational cost of propagating the coupled channel wave packets in the body frame scales approximately as N3/2 where N is the total number of channels. For large numbers of channels, this will be much more efficient than the space frame CCWP method previously developed which scales approximately as N2 under the same conditions. Timing results are reported for a model system for 25, 64, 144, 256, and 969 channels. The calculations were run with total J=30 and with parameters corresponding to a heavy diatom. The results for some representative transitions are compared to the identical transitions obtained using the space frame formalism. For all values of N, the body frame computations ran faster than the corresponding ones using the space frame, with the ratio increasing to a value of 4.5 for 969 channels. This is a significant improvement which will continue to increase with N, encouraging us to believe that the body frame CCWP method will prove practical for calculating scattering information for more realistic inelastic and reactive systems.

Notes: The first probe measurements of edge turbulence and transport in a neutral beam induced high confinement mode (H-mode) are reported. A strong negative radial electric field is directly observed in H-mode. A transient suppression of normalized ion saturation and floating potential fluctuation levels occurs at the low confinement mode to high confinement mode (L–H) transition, followed by a recovery to near low mode (L-mode) levels. The average poloidal wave number and the poloidal wave-number spectral width are decreased, and the correlation between fluctuating density and potential is reduced. A large-amplitude coherent oscillation, localized to the strong radial electric field region, is observed in H-mode but does not cause transport. In H-mode the effective turbulent diffusion coefficient is reduced by an order of magnitude inside the last closed flux surface and in the scrape-off layer. The results are compared with a heuristic model of turbulence suppression by velocity-shear stabilization.

Notes: The crystal structure and magnetoresistance of the polycrystalline La1−xLixMnO3 (x=0.10, 0.15, 0.20, 0.30) are investigated. The result of the Rietveld refinement of x-ray powder diffraction shows that the room temperature structural transition from rhombohedral (R3¯C) to orthorhombic (Pbnm) symmetry occurs at the Li-doped level x≥0.2. Accompanying the occurrence of the structural transition, the lattice distortion and the bending of the Mn–O–Mn bond increase and the ferromagnetic transition temperature TC decreases. For x=0.10 and 0.15 samples, double metal–insulator (M–I) transitions accompanying a single ferromagnetic transition and a negative magnetoresistance as high as 26% in a magnetic field of 0.8 T are observed. For x=0.20 and 0.30, the samples manifest nonmetallic behavior throughout the measured temperature range. We suggest that the double M–I transitions phenomena of low Li-doped samples originate from the magnetic inhomogeneity due to the formations of the Mn3+ and Mn4+-rich regions induced by partial substitution of the monovalent Li1+ ions for the trivalent La3+ ions. The transport property of high Li-doped samples (x=0.20 and 0.30) can be explained according to the additional localization of eg electrons induced by a static coherent Jahn–Teller distortion of the MnO6 octahedra stemming from the structural transition from rhombohedral (R3¯C) to orthorhombic (Pbnm) and the reduced bandwidth of eg electrons due to the increased bending of the Mn–O–Mn bond. © 2000 American Institute of Physics.

Notes: Abstract: In response to axonal injury, noradrenergic sympathetic neurons of the adult superior cervical ganglion (SCG) alter their neurotransmitter phenotype. These alterations include increases in the levels of the neuropeptides, galanin, vasoactive intestinal peptide (VIP), and substance P (SP) and a decrease in the catecholamine biosynthetic enzyme tyrosine hydroxylase (TH). Previous studies have indicated that after axotomy in vivo, leukemia inhibitory factor (LIF) plays an important role in increasing the contents of galanin and VIP in the SCG. In the present study, by examining the time courses of the changes in LIF and neuropeptide mRNA and by using LIF null mutant mice, we have determined that LIF alters neuropeptide content in part by increasing levels of peptide mRNA. In addition, LIF also makes a small contribution to the axotomy-induced down-regulation of mRNA encoding TH and neuropeptide Y, both of which are normally expressed at high levels in the SCG. Finally, by using a LIF-blocking antiserum, this cytokine was found to regulate SP expression in an in vitro axonal injury model. Thus, after axotomy, a single factor, LIF, participates in the down-regulation of peptides/proteins involved in normal neurotransmission and the up-regulation of a group of neuropeptides normally not present in the SCG that may be involved in regeneration.