Extreme ultraviolet line emission at 24.7 nm from Li-like nitrogen plasma produced by a short KrF excimer laser pulse

Recently using KrF high power laser (248 nm; 350 fs; 5.0x10(16) W/cm(2)) in the Rutherford Appleton Laboratory an experimental search for recombination extreme ultraviolet (XUV) laser action in Li-like nitrogen ions was performed. To understand the experimental results of line emission at 24.7 nm in the 3d(5/2)-2p(3/2) transition of the Li-like nitrogen ion a simulation was undertaken using a one-dimensional Lagrangian hydrodynamic code. From the simulation results, we confirmed that there was nonlinear dependence of spectral line emission on the gas density which was well matched to the experimental results. Only a six times increase of the 24.7 nm emission intensity was obtained when the plasma length was increased 1000 times from 1 mu m as an optically thin case to 1 mm. Also, the spatial profile of the electron density and temperature was obtained and the electron temperature was about 40-50 eV which was too high for the optical field ionization x-ray lasing. We could not find evidence of x-ray laser gain. (C) 1996 American Institute of Physics.

Investigating the dynamics of laser induced sparks in atmospheric helium using Rayleigh and Thomson scattering

We have used optical Rayleigh and Thomson scattering to investigate the expansion dynamics of laser induced plasma in atmospheric helium and to map its electron parameters both in time and space. The plasma is created using 9 ns duration, 140 mJ pulses from a Nd:YAG laser operating at 1064 nm, focused with a 10 cm focal length lens, and probed with 7 ns, 80 mJ, and 532 nm Nd:YAG laser pulses. Between 0.4 μs and 22.5 μs after breakdown, the electron density decreases from 3.3 × 1017 cm−3 to 9 × 1013 cm−3, while the temperature drops from 3.2 eV to 0.1 eV. Spatially resolved Thomson scattering data recorded up to 17.5 μs reveal that during this time the laser induced plasma expands at a rate given by R ∼ t0.4 consistent with a non-radiative spherical blast wave. This data also indicate the development of a toroidal structure in the lateral profile of both electron temperature and density. Rayleigh scattering data show that the gas density decreases in the center of the expanding plasma with a central scattering peak reemerging after about 12 μs. We have utilized a zero dimensional kinetic global model to identify the dominant particle species versus delay time and this indicates that metastable helium and the He2 + molecular ion play an important role.

New design of a multi-jet target for quasi phase matching

An improved dual-gas quasi-phase matching (QPM) foil target for high harmonic generation (HHG) is presented. The target can be setup with 12 individual gas inlets each feeding multiple nozzles separated by a minimum distance of 10 μm. Three-dimensional gas density profiles of these jets were measured using a Mach-Zehnder Interferometer. These measurements reveal how the jets influence the density of gas in adjacent jets and how this leads to increased local gas densities. The analysis shows that the gas profiles of the jets are well defined up to a distance of about 300 μm from the orifice. This target design offers experimental flexibility, not only for HHG/QPM investigations, but also for a wide range of experiments due to the large number of possible jet configurations. We demonstrate the application to controlled phase tuning in the extreme ultraviolet using a 1 kHz-10 mJ-30 fs-laser system where interference between two jets in the spectral range from 17 to 30 nm was observed.

Developed turbulence and nonlinear amplification of magnetic fields in laboratory and astrophysical plasmas

The visible matter in the universe is turbulent and magnetized. Turbulence in galaxy clusters is produced by mergers and by jets of the central galaxies and believed responsible for the amplification of magnetic fields. We report on experiments looking at the collision of two laser-produced plasma clouds, mimicking, in the laboratory, a cluster merger event. By measuring the spectrum of the density fluctuations, we infer developed, Kolmogorov-like turbulence. From spectral line broadening, we estimate a level of turbulence consistent with turbulent heating balancing radiative cooling, as it likely does in galaxy clusters. We show that the magnetic field is amplified by turbulent motions, reaching a nonlinear regime that is a precursor to turbulent dynamo. Thus, our experiment provides a promising platform for understanding the structure of turbulence and the amplification of magnetic fields in the universe.

Density-Enhanced Gas and Dust Shells in a New Chemical Model for IRC+10216

A new chemical model is presented for the carbon-rich circumstellar envelope (CSE) of the asymptotic giant branch star IRC+10216. The model includes shells of matter with densities that are enhanced relative to the surrounding circumstellar medium. The chemical model uses an updated reaction network including reactions from the RATE06 database and a more detailed anion chemistry. In particular, new mechanisms are considered for the formation of CN-, C3N-, and C2H-, and for the reactions of hydrocarbon anions with atomic nitrogen and with the most abundant cations in the CSE. New reactions involving H- are included which result in the production of significant amounts of C2H- and CN- in the inner envelope. The calculated radial molecular abundance profiles for the hydrocarbons C2H, C4H, and C6H and the cyanopolyynes HC3N and HC5N show narrow peaks which are in better agreement with observations than previous models. Thus, the narrow rings observed in molecular microwave emission surrounding IRC+10216 are interpreted as arising in regions of the envelope where the gas and dust densities are greater than the surrounding circumstellar medium. Our models show that CN- and C2H- may be detectable in IRC+10216 despite the very low theorized radiative electron attachment rates of their parent neutral species. We also show that magnesium isocyanide (MgNC) can be formed in the outer envelope through radiative association involving Mg+ and the cyanopolyyne species.

New insight into mechanisms in water-gas-shift reaction on Au/CeO2(111): A density functional theory and kinetic study

Using density functional theory (DFT) and kinetic analyses, a new carboxyl mechanism for the water-gas-shift reaction (WGSR) on Au/CeO2(111) is proposed. Many elementary steps in the WGSR are studied using an Au cluster supported on CeO2(111). It is found that (i) water can readily dissociate at the interface between Au and CeO2; (ii) CO2 can be produced via two steps: adsorbed CO on the Au cluster reacts with active OH on ceria to form the carboxyl (COOH) species and then COOH reacts with OH to release CO2; and (iii) two adsorbed H atoms recombine to form molecular H-2 on the Au cluster. Our kinetic analyses show that the turnover frequency of the carboxyl mechanism is consistent with the experimental one while the rates of redox and formate mechanisms are much slower than that of carboxyl mechanism. It is suggested that the carboxyl pathway is likely to be responsible for WGSR on Au/CeO2.

Examining the redox and formate mechanisms for water-gas shift reaction on Au/CeO2 using density functional theory

We perform DFT calculations to investigate the redox and formate mechanisms of water-gas-shift (WGS) reaction on Au/CeO2 catalysts. In the redox mechanism, we analyze all the key elementary steps and find that the OH cleavage is the key step. Three possible pathways of OH cleavage are calculated: (1) OHad '' + *'--> H-ad' + O-ad"; (2) H-ad' + OHad '' --> H-2(g) + O-ad '' + *'; and (3) OHad" + OHad '' --> 2O(ad '') + H-2(g) (*': the free adsorption sites on the oxides; ad': adsorption on the metal; ad": adsorption on the oxide, respectively). In the formate mechanism, we identify all the possible pathways for the formation and decomposition of surface formates in the WGS reaction. It is found that there is a shortcoming in the redox and formate mechanisms which is related to surface oxygen reproduction. Four possible pathways for producing surface oxygen are studied, and all the barriers of the four pathways are more than 1 eV. Our results suggest that the processes to reproduce surface oxygen in the reaction circle are not kinetically easy. (C) 2008 Elsevier B.V. All rights reserved.

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

Neutral gas depletion mechanisms in dense low-temperature argon plasmas

Neutral gas depletion mechanisms are investigated in a dense low-temperature argon plasma-an inductively coupled magnetic neutral loop (NL) discharge. Gas temperatures are deduced from the Doppler profile of the 772.38 nm line absorbed by argon metastable atoms. Electron density and temperature measurements reveal that at pressures below 0.1 Pa, relatively high degrees of ionization (exceeding 1%) result in electron pressures, p(e) = kT(e)n(e), exceeding the neutral gas pressure. In this regime, neutral dynamics has to be taken into account and depletion through comparatively high ionization rates becomes important. This additional depletion mechanism can be spatially separated due to non-uniform electron temperature and density profiles (non-uniform ionization rate), while the gas temperature is rather uniform within the discharge region. Spatial profiles of the depletion of metastable argon atoms in the NL region are observed by laser induced fluorescence spectroscopy. In this region, the depletion of ground state argon atoms is expected to be even more pronounced since in the investigated high electron density regime the ratio of metastable and ground state argon atom densities is governed by the electron temperature, which peaks in the NL region. This neutral gas depletion is attributed to a high ionization rate in the NL zone and fast ion loss through ambipolar diffusion along the magnetic field lines. This is totally different from what is observed at pressures above 10 Pa where the degree of ionization is relatively low (

Dramatic liquid-phase dehydrogenation rate enhancements using gas-phase hydrogen acceptors

The dehydrogenation of 1,2,3,4-tetrahydrocarbazole (THCZ) to form carbazole (CZ) over supported palladium catalysts was examined in the presence of hydrogen acceptors. As expected, liquid hydrogen acceptors increased the rate of reaction but, importantly, gaseous hydrogen acceptors also have been used. Ethene, propene, and but-1-ene showed up to a fivefold increase in the rate of dehydrogenation. Moreover, compared with the analogous liquid systems, the gaseous alternatives are a potentially more economic method of enhancing the activity and provide a simpler workup. The mechanism for the increase in rate was examined by density functional theory calculations, which showed that the propene hydrogenation competes effectively with the back-hydrogenation of the intermediates formed during the THCZ dehydrogenation, resulting in a shift in the equilibrium toward to the formation of CZ. (C) 2007 Elsevier Inc. All rights reserved.

Au on (111) and (110) surfaces of CeO2: A density-functional theory study

The atomic structures of gold supported on (111) and (110) surfaces of CeO2 have been studied using density-functional theory calculations. A single Au atom is placed on three adsorption sites on the surfaces; the stoichiometric surfaces, an oxygen vacancy and a Ce-vacancy. It is found that (i) the Au adsorption energies are in the following order: E-ad(Ce-vacancy) > E-ad(O-vacancy) > E-ad(stoichiometric surface); and (ii) the Au atom adsorption on the Ce-vacancy activates O atoms nearby. One 0 atom is less stable than that in O-2 in the gas phase and another O atom is much easier to remove compared to that of the stoichiometric surfaces. These results suggest that the Au adsorption on Ce-vacancies not only creates an O-vacancy but also activates an O atom nearby. This provides a piece of direct evidence that Au adsorption on a Ce-vacancy may be responsible for some unique catalytic properties of Au/CeO2. (C) 2008 Elsevier B.V. All rights reserved.

CO dissociation and O removal on Co(0001): a density functional theory study

CO dissociation and O removal (water formation) are two important processes in the Fischer-Tropsch synthesis. In this study, both processes are studied on the flat and stepped Co(0 0 0 1) using density functional theory. It is found that (i) it is difficult for CO to dissociate on the flat Co(0 0 0 1) due to the high barrier of 1.04 eV relative to the CO molecule in the gas phase; (ii) the stepped Co(0 0 0 1) is much more favoured for CO dissociation; (iii) the first step in water formation, O + H --> OH, is unlikely to occur on the flat Co(0 0 0 1) due to the high barrier of 1.72 eV, however, this reaction can become feasible on steps where the barrier is reduced to 0.73 eV; and (iv) the barrier in the second step, OH + H --> H2O, on steps is higher than that on the flat surface. (C) 2004 Elsevier B.V. All rights reserved.

Absolute Calibration of Atomic Density Measurements by Laser-Induced Fluorescence Spectroscopy with Two-Photon Excitation (TALIF)

The two-photon resonances of atomic hydrogen (? = 2 × 205.1 nm), atomic nitrogen (? = 2 × 206.6 nm) and atomic oxygen (? = 2 × 225.6 nm) are investigated together with two selected transitions in krypton (? = 2×204.2 nm) and xenon (? = 2×225.5 nm). The natural lifetimes of the excited states, quenching coefficients for the most important collisions partners, and the relevant ratios of the two-photon excitation cross sections are measured. These data can be applied to provide a calibration for two-photon laser-induced fluorescence measurements based on comparisons with spectrally neighbouring noble gas resonances.

Absolute Atomic Oxygen Density Measurements by Two-Photon Absorption Laser-induced Fluorescence Spectroscopy in an RF-Excited Atmospheric Pressure Plasma Jet

The atmospheric pressure plasma jet is a capacitively coupled radio frequency discharge (13.56 MHz) running with a high helium flux (2m3 h-1) between concentric electrodes. Small amounts (0.5%) of admixed molecular oxygen do not disturb the homogeneous plasma discharge. The jet effluent leaving the discharge through the ring-shaped nozzle contains high concentrations of radicals at a low gas temperature—the key property for a variety of applications aiming at treatment of thermally sensitive surfaces. We report on absolute atomic oxygen density measurements by two-photon absorption laser-induced fluorescence (TALIF) spectroscopy in the jet effluent. Calibration is performed with the aid of a comparative TALIF measurement with xenon. An excitation scheme (different from the one earlier published) providing spectral matching of both the two-photon resonances and the fluorescence transitions is applied.

Absolute Atomic Oxygen Density Distributions in the Effluent of a Micro Scale Atmospheric Pressure Plasma Jet

The coplanar microscale atmospheric pressure plasma jet (µ-APPJ) is a capacitively coupled radio frequency discharge (13.56 MHz, ~15W rf power) designed for optimized optical diagnostic access. It is operated in a homogeneous glow mode with a noble gas flow (1.4 slm He) containing a small admixture of molecular oxygen (~0.5%). Ground state atomic oxygen densities in the effluent up to 2 × 1014 cm-3 are measured by two-photon absorption laser-induced fluorescence spectroscopy (TALIF) providing space resolved density maps. The quantitative calibration of the TALIF setup is performed by comparative measurements with xenon. A maximum of the atomic oxygen density is observed for 0.6% molecular oxygen admixture. Furthermore, an increase in the rf power up to about 15W (depending on gas flow and mixture) leads to an increase in the effluent’s atomic oxygen density, then reaching a constant level for higher powers.