Vibrational excitation in some four-center transition states.
Substitution rates for homogeneous deuterium- hydrogen exchange reactions controlled by vibrational excitation
GAS EXCHANGE↗
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High resolution infrared astronomy satellite observations of a selected spiral galaxy
The H I, infrared, CO, H alpha and H beta band observations of M51, the prototypical grand-design spiral galaxy, are used to study the consequences of star formation for the distribution of H I and dust. Using the new Very Large Array (VLA) map of 21 cm emission, the Owens Valley Radio Observatory CO mosaic map, and an H alpha imate, new tests were performed with the idea of Tilanus and Allen that the H I is largely a photodissociation product in star-forming regions. It is confirmed that the H I spiral arms are generally coincident with the H II region arms, and offset downstream from the CO arms. The radial distributions of total gas, H alpha and H I surface density have a simple explanation in the dissociation picture. The distributions also demonstrate how the surface density of H I might be related to the star formation efficiency in molecule-rich galaxies. The large width of the H I regions along the arms compared to that of the giant H II regions can be understood in terms of a simple calculation of the expected size of an H I region associated with a typical giant H II region. The longer lifetime of the stars producing dissociating radiation vs. those producing ionizing radiation and the relatively long molecular formation timescale will also contribute to the greater width of the H I arms if stars are continuously forming on the arms. The lack of detailed coincidence of the H I and H II regions along the inner arms has a variety of possible explanations. Two simple tests were performed to probe the origins of the IRAS emission in M51. First, it was found that the infrared excess (IFE) of M51 is 24, suggesting that a substantial fraction of the infrared emission arises from dust heated by photons which do not originate in massive star-formaing regions. Second, radial cuts through the IRAS bands show that at 12, 25, and 60 microns, the arm-interarm contrast of the IRAS emission is substantially less than that of the H alpha emission, providing further evidence for the explanation and for the existence of a broadly distributed dust component. Deconvolved IRAS maps have improved resolution but do not change this finding.
Kulkarni, S. R.↗
Three-dimensional rarefied flow simulations for the Aeroassist Flight Experiment vehicle
Hypersonic rarefied flow about the Aeroassist Flight Experiment vehicle has been investigated using a three-dimensional direct simulation Monte Carlo method. Calculations are performed for the transitional flows encountered during the vehicle's atmospheric entry for altitudes of 110 and 100 km with an entry velocity of 9.9 km/s. The simulations are performed using a five-species reacting gas model that account for rotational and vibrational internal energies. The solutions indicate that dissociation is important at altitudes of 110 km and below. Results are presented for surface pressures, convective heating, flowfield structure, and aerodynamic coefficient variations with altitude.
Celenligil, M. Cevdet↗
Radiative shocks and nonequilibrium chemistry in the early universe - Galaxy and primordial star formation
The nonequilibrium radiative cooling, recombination, and molecule formation behind steady-state shock waves in primordial composition gas is studied. The hydrodynamical conservation equations are solved as well as equations for nonequilibrium ionization, recombination, and molecule formation and the equation of radiative transfer. The shocked gas is found to cool faster than it can recombine; as a result it is able to form an H2 concentration as high as 0.001 or higher via the formation of H(-) and H2(+) intermediaries due to the enhanced nonequilibrium ionization at 10,000 K. With such an H2 concentration, the gas cools by rotational-vibrational line excitation of H2 molecules to well below the canonical final temperature of 10,000 K for a molecule-free gas without metals. It is shown that, as the level of external ionizing and dissociating radiation flux is increased, the formation of and cooling by H2 molecules can be inhibited and delayed.
Shapiro, Paul R.↗
Design, Synthesis, and Characterization of Polymer Precursors to Li x PON and Li x SiPON Glasses: Materials That Enable All-Solid-State Batteries (ASBs)
LiPON-like glasses that form lithium dendrite impenetrable interfaces between lithium battery components are enabling materials that may replace liquid electrolytes permitting production of all-solid-state batteries (ASBs). Unfortunately, to date, such materials are introduced only via gas-phase deposition. Furthermore, we demonstrate the design and synthesis of easily scaled, lowtemperature, low-cost, solution-processable inorganic polymers containing LiPON/LiSiPON elements. OPCl 3 and hexachlorophosphazene [Cl 2 P=N] 3 provide starting points for elaboration using MNH 2 (M = Li/Na) or (Me 3 Si)NH followed by reaction with controlled amounts of LiNH 2 to produce oligomers/polymers with molecular weights (MWs) ≈1–2 kDa characterized by multinuclear NMR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and matrix-assisted laser desorption/ ionization (MALDI)-time-of-flight (ToF) offering stabilities to 150–200 °C and ceramic yields (800 °C) of 50–60%. 7 Li NMR suggests that precursor-bound Li + dissociates easily, beneficial for electrochemical applications. XPS shows higher N/P ratios (1–3) than via gas-phase methods (<1) correlating N/P ratios, 7 Li shifts, and Li + conductivities. Li 2 SiPHN offers the highest ambient conductivity of 3 × 10 –1 mS cm –1 at 400 °C/2 h/N 2 .
36 MATERIALS SCIENCE↗
Gas-phase negative ion photoelectron spectroscopy and reactivity of phenylacetylide
Arylacetylides such as phenylacetylide (PhCC–, 1) are important nucleophiles used in synthetic chemistry yet rarely have they been studied as bare carbanions. In this work, the phenylacetylide anion was formed via electrospray ionization (ESI) or multistage mass spectrometry (MSn) experiments and subsequently examined in the gas phase by negative ion photoelectron spectroscopy (NIPES), ion-molecule reactions (IMR), alongside theoretical calculations to probe its fundamental structure and reactivity. Photoelectron spectra of PhCC– (1) revealed vertical (VDE) and adiabatic detachment energies (ADE), both of 3.220 eV. The latter value is also the electron affinity (EA) of the phenylethynyl radical (PhCC•) from which a bond dissociation energy (BDE) of phenylacetylene (PhCCH) was derived to be ca. 131.3 ± 1.7 kcal mol-1 using a gas-phase thermochemical cycle. Detachment of an electron from PhCC– at 266 nm likely results in resonant autodetachment, supported by Franck-Condon Factor (FCF) simulations. The phenylacetylide anion reacts with methyl iodide (CH3I) and allyl iodide (C3H5I) via SN2 nucleophilic displacement with measured rate coefficients of 4.29 and 3.66 × 10-10 cm3 molecule-1 s-1, respectively. The mechanisms associated with these displacement reactions are explained and understood in terms of the reaction kinetics, natural bond orbital (NBO) theory, and Density Functional Theory (DFT) calculations.
Ma, Howard Z.↗
Understanding methanol dissociative adsorption and oxidation on amorphous oxide films
Interactions between a transition metal (oxide) catalyst and a support can tailor the number and nature of active sites, for instance in the methanol oxidation reaction.In this report we use ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify and compare the surface adsorbates that form on amorphous metal oxide films that maximize such interactions. Considering Al (1−x) M x O y (M = Fe or Mn) films at a range of methanol : oxygen gas ratios and temperatures, we find that the redox-active transition metal site (characterized by methoxy formation) dominates dissociative methanol adsorption, while basic oxygen sites (characterized by carbonate formation) play a lesser role. Product detection, however, indicates complete oxidation to carbon dioxide and water with partial oxidation products (dimethyl ether) comprising a minor species. Comparing the intensity of methoxy and hydroxyl features at a fixed XPS chemical shift suggests methanol deprotonation during adsorption in oxygen rich conditions for high transition metal content. However, increasing methanol partial pressure and lower metal site density may promote oxygen vacancy formation and the dehydroxylation pathway, supported by a nominal reduction in the oxidation state of iron sites. These findings illustrate that AP-XPS and mass spectrometry together are powerful tools in understanding metal–support interactions, quantifying and probing the nature of catalytic active sites, and considering the link between electronic structure of materials and their catalytic activity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
CH 3 Radical Generation in Microplasmas for Up-Conversion of Methane
The conversion of methane, CH 4 , into higher value chemicals using low temperature plasmas is challenged by both improving efficiency and selectivity. One path towards selectivity is capturing plasma produced methyl radicals, CH 3 , in a solvent for aqueous processing. Due to the rapid reactions of methyl radicals in the gas phase, the transport distance from production of the CH 3 to its solvation should be short, which then motivates the use of microplasmas. The generation of CH 3 in Ar/CH 4 /H 2 O plasmas produced in nanosecond pulsed dielectric barrier discharge microplasmas is discussed using results from a computational investigation. The microplasma is sustained in the channel of a microfluidic chip in which the solvent flows along one wall or in droplets. CH 3 is primarily produced by electron-impact of and dissociative excitation transfer to CH 4 , as well as CH 2 reacting with CH 4 . CH 3 is rapidly consumed to form C 2 H 6 which, in spite of being subject to these same dissociative processes, accumulates over time, as do other stable products including C 3 H 8 and CH 3 OH. The gas mixture and electrical properties were varied to assess their effects on CH 3 production. CH 3 production is largest with 5% CH 4 in the Ar/CH 4 /H 2 O mixture due to an optimal balance of electron-impact dissociation, which increases with CH 4 percentage, and dissociative excitation transfer and CH 2 reacting with CH 4 , which decrease with CH 4 percentage. Design parameters of the microchannels were also investigated. Increasing the permittivity of the dielectrics in contact with the plasma increased the ionization wave intensity which increased CH 3 production. Increased energy deposition per pulse generally increased CH 3 production as does lengthening pulse length up to a certain point. The arrangement of the solvent flow in the microchannel can also affect the CH 3 density and fluence to the solvent. The fluence of CH 3 to the liquid solvent is increased if the liquid is immersed in the plasma as a droplet or is a layer on the wall where the ionization wave terminates. The solvation dynamics of CH 3 with varying numbers of droplets was also examined. Here, the maximum density of solvated methyl radicals CH 3aq occurs with a large number of droplets in the plasma. However, the solvated CH 3aq density can rapidly decrease due to desolvation, emphasizing the need to quickly react the solvated species in the solvent.
03 NATURAL GAS↗
Etching of Si 3 N 4 induced by electron beam plasma from hollow cathode plasma in a downstream reactive environment
An etching system based on the interaction of electrons extracted from a direct current (DC) hollow-cathode (HC) Ar plasma and injected towards a Si3N4 covered silicon substrate located in the downstream reactive environment created by an additional remote CF 4 /O 2 plasma source was developed and evaluated. By controlling the properties of the injected beam electrons, this approach allows to deliver energy to a surface functionalized by exposure to reactive species, and initiate surface etching. The energy of the primary beam electrons is controlled by the acceleration voltage relative to the HC discharge. Ar atoms flow from the high-pressure HC discharge into the low pressure downstream reactive environment in the process chamber. For an acceleration voltage greater than the ionization potential of Ar and/or process gas species, the energetic primary beam electrons produce a secondary plasma in the process chamber, and can also cause additional dissociation. We have characterized the properties of the secondary plasma and also surface etching of Si 3 N 4 as a function of process parameters, including acceleration voltage (0-80 V), discharge current of the HC discharge (1-2 A), pressure (3.5-20 mTorr), source to substrate distance (1.5 to 5 cm), and feed gas composition (20% and 80% O2 in CF 4 /O 2 ). The electron energy probability function (EEPF) measured with a Langmuir probe about 2.5 cm below the extraction ring suggests several major groups of electrons for this situation, including high energy primary beam electrons with an energy that varies as the acceleration voltage is changed and low energy electrons produced by beam electron-induced ionization of the Ar gas in the process chamber. When a remote CF 4 /O 2 plasma is additionally coupled to the process chamber, Si 3 N 4 surfaces can be functionalized, and by varying the energy of the beam electrons, Si 3 N 4 etching can be induced by electron-neutral synergy effect with plasma-surface interaction. For conditions without beam electron injection, the remote plasma etching rate (ER) of Si 3 N 4 depends strongly on the O 2 concentration in the CF 4 /O 2 processing gas mixture and can be suppressed for O 2 -rich process conditions by the formation of a SiONF passivation layer on the Si 3 N 4 surface. The combination of the HC electron beam source with the remote plasma source (HCEB-RP) makes it possible to induce Si 3 N 4 etching for O 2 -rich remote plasma conditions where remote plasma by itself produces negligible Si 3 N 4 etching. The electron enhanced etching of Si 3 N 4 depends strongly on O 2 /CF 4 mixing ratio reflecting changing arrival rates of O and F species at the surface. Optical emission spectroscopy was used to estimate the ratio of gas phase F and O densities and found to be controlled by the gas mixing ratio and independent of HC EB operating conditions. At this time the detailed sequence of events operative in the etching mechanism is unclear. While the increase of the electron energy is ultimately responsible for initiating surface etching, at present we cannot rule out a role of ions from the simultaneously produced secondary plasma in plasma surface interaction mechanisms.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Correlating the Reverse Water–Gas Shift Reaction with Surface Chemistry: The Influence of Reactant Gas Exposure to Ni(100)
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Experimental and computational results for 5 degree blunt cones with shock generators at high velocity
Experiments and computations have been performed under laminar conditions in air on 5-deg blunt cones at velocities of 5 km/s and 6 km/s and at Reynolds numbers of 100,000 and 1 million. The computations were performed using ideal-, equilibrium- and nonequilibrium-chemistry models for air. At the conditions of the tests, the aerodynamic coefficients are sensitive to the real-gas effects present, and both experimental and computational aerodynamic coefficients show real-gas and nonlinear effects. The nonequilibrium computations show that a large amount of oxygen is dissociated in the blunt nose region of the flow and much of the oxygen remains dissociated over the entire length of the body, providing an insight into the source of the observed effects in the aerodynamic coefficients. The experimental and computational shock-shapes are in good agreement.
Strawa, A. W.↗
Research activity at the shock tube facility at NASA Ames
The real gas phenomena dominate the relaxation process occurring in the flow around hypersonic vehicles. The air flow around these vehicles undergoes vibrational excitation, chemical dissociation, and ionization. These chemical and kinetic phenomena absorb energy, change compressibility, cause temperature to fall, and density to rise. In high-altitude, low density environments, the characteristic thicknesses of the shock layers can be smaller than the relaxation distances required for the gas to attain chemical and thermodynamic equilibrium. To determine the effects of chemical nonequilibrium over a realistic hypersonic vehicle, it would be desirable to conduct an experiment in which all aspects of fluid flow are simulated. Such an experiment is extremely difficult to setup. The only practical alternative is to develop a theoretical model of the phenomena and to compute the flow around the vehicle including the chemical nonequilibrium, and compare the results with the experiments conducted in the facilities under conditions where only a portion of the flow phenomena is simulated. Three types of experimental data are needed to assist the aerospace community in this model development process: (1) data which will enhance our phenomenological understanding of the relaxation process, (2) data on rate reactions for the relevant reactions, and (3) data on bulk properties, such as spectral radiation emitted by the gas, for a given set of aerodynamic conditions. NASA Ames is in a process of collecting such data by simulating the required aerothermochemical conditions in an electric arc driven shock tube.
Sharma, Surendra P.↗
Computer program of data reduction procedures for facilities using CO2-N2-O2-Ar equilibrium real-gas mixtures
Data reduction procedures for determining free-stream and post-normal-shock flow conditions are presented. These procedures are applicable to flows of CO2, N2, O2, Ar, or mixtures of these gases and include the effects of dissociation and ionization. The assumption of thermochemical equilibrium free-stream and post-normal-shock flow is made. Although derived primarily to meet the immediate needs of an expansion tube of a hot gas radiation research facility, these procedures are applicable to any supersonic or hypersonic test facility using these gases or mixtures thereof. The data reduction procedures are based on combinations of three of the following flow parameters measured in the immediate vicinity of the test section: (1) stagnation pressure behind normal shock, (2) free-stream static pressure, (3) stagnation-point heat-transfer rate, (4) free-stream velocity, and (5) free-stream density. Thus, these procedures do not depend explicitly upon measured or calculated upstream flow parameters. The procedures are incorporated into a single computer program written in FORTRAN IV language. A listing of this computer program is presented, along with a description of the inputs required and a sample of the data printout.
Miller, C. G., III↗
Plasma-assisted catalysis for ammonia synthesis in a dielectric barrier discharge reactor: key surface reaction steps and potential causes of low energy yield
Ammonia synthesis experiments were carried out in a coaxial dielectric barrier discharge (DBD) reactor packed with several different supports and metal catalysts. There was a marked increase in the reaction rate, over that obtained in an empty DBD plasma reactor, upon introduction of a packed bed of γ-Al 2 O 3 , Ru/γ-Al 2 O 3 , or SiO 2 particles. The difference in the reaction rates over γ-Al 2 O 3 and Ru/γ-Al 2 O 3 was minimal. Complementary zero-dimensional plasma kinetic model analysis was also performed using inputs from experimental data. This kinetic analysis allowed for gas phase reactions, Eley–Rideal (E–R) reactions, and direct adsorption of radical species on the γ-Al 2 O 3 surface. On the metal surface, dissociative adsorption of N 2 and H 2 , and Langmuir–Hinshelwood reactions were also included. This analysis revealed that, under the conditions of our experiments, ammonia synthesis proceeds principally by the formation of reactive radicals in the gas phase, which then adsorb and participate in E–R reactions on both the metal and support material surfaces. Furthermore, this finding illustrates a challenge for substantially increasing the energy yield for plasma-assisted ammonia synthesis in typical DBD reactors containing packed catalyst beads.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Experimental study of atmospheric pressure single-pulse nanosecond discharge in pin-to-pin configuration
We present an experimental study of nanosecond high-voltage discharges in a pin-to-pin electrode configuration at atmospheric conditions operating in single-pulse mode (no memory effects). Discharge parameters were measured using microwave Rayleigh scattering, laser Rayleigh scattering, optical emission spectroscopy enhanced with a nanosecond probing pulse, and fast photography. Spark and corona discharge regimes were studied for electrode gap sizes 2-10 mm and discharge pulse duration of 90 ns. The spark regime was observed for gaps < 6 mm using discharge pulse energies of 0.6-1 mJ per mm of the gap length. Higher electron number densities, total electron number per gap length, discharge currents, and gas temperatures were observed for smaller electrode gaps and larger pulse energies, reaching maximal values of about 7.5 x 10 15 cm -3 , 3.5 x 10 11 electrons per mm, 22 A, and 4,000 K (at 10 microseconds after the discharge), respectively, for a 2 mm gap and 1 mJ/mm discharge pulse energy. Initial breakdown was followed by a secondary breakdown occurring about 30-70 ns later and was associated with ignition of a cathode spot and transition to cathodic arc. Here, a majority of the discharge pulse energy was deposited into the gas before the secondary breakdown (85-89%). The electron number density after the ns-discharge pulse decayed with a characteristic time scale of 150 ns governed by dissociative recombination and electron attachment to oxygen mechanisms. For the corona regime, substantially lower pulse energies (~0.1 mJ/mm), peak conduction current (1-2 A), and electron numbers (3-5 x 10 10 electrons per mm), and gas temperatures (360 K) were observed.
42 ENGINEERING↗
In Situ Studies of Methanol Decomposition Over Cu(111) and Cu2O/Cu(111): Effects of Reactant Pressure, Surface Morphology, and Hot Spots of Active Sites
The dissociative adsorption of methanol was investigated on Cu(111) and ultrathin Cu 2 O films. We employed synchrotron-based Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Scanning Tunneling Microscopy (STM) to study the dynamics of gas–solid interactions, and calculations based on Density Functional Theory (DFT) were used to examine the reaction path. C 1s XPS spectra revealed that methanol underwent dissociative adsorption on plain Cu(111) to form methoxy (CH 3 O), formaldehyde (H 2 CO), and formate (HCOO) at a pressure range of 0.5–10 mTorr, with these species remaining on the surface after evacuation. This was accompanied by the appearance of a low coverage (~0.05 ML) of O ads in the O 1s which can be considered a highly active site for methanol activation. The high activity is apparent by a coverage of 0.8 ML of methoxy at room temperature. STM was unable to image these species at room temperature as they were highly mobile on metallic copper. In contrast, for CH 3 OH on Cu 2 O/Cu(111), STM showed clear hot spots for reaction and a complex array of adsorption structures. On the oxide substrate, there was decomposition of methanol to H 2 CO, CH 3 O, HCOO, and hydrocarbon species (CH x ) due to the subsequent interactions of methanol with lattice oxygen. Cu(111) remained entirely saturated with decomposition products under 10 mTorr of methanol (θ ≈ 0.97 ML), whereas the Cu 2 O overlayer was saturated at a much lower coverage (θ ≈ 0.30 ML). STM revealed rows and step edges of Cu 2 O decorated with decomposition products and metallic Cu islands ~5 nm in size. The difference in activity between Cu(111) and Cu 2 O/Cu(111) is attributed to the significant amount of O present on the oxide surface. Additionally, Density Functional theory (DFT) calculations described the XPS measurements well, showing a likely methanol dissociation to *CH 3 O and therefore a surface reduction. More importantly, the DFT results revealed that it was the chemisorbed oxygen on Cu 2 O/Cu(111) which oxidized the dissociated *CH 3 O to *HCOO and eventually CO 2 , while the reaction only involving upper oxygen on the Cu 2 O hexagonal ring led to the formation of H 2 CO.
36 MATERIALS SCIENCE↗
Abundances of simple oxygen-bearing molecules and ions in interstellar clouds
The abundances of simple oxygen-bearing interstellar molecules in warm (T at least 40 K), diffuse, and moderately thick clouds are calculated on the basis of binary gas-phase reactions. The most important reactions are ion-molecule, charge-exchange, and dissociative-recombination reactions, as suggested mainly by earlier workers. The progenitor of these molecules in diffuse clouds is the cosmic-ray-produced H(+) ion, working through the charge-exchange reaction with O. The ionization of H(+) and He(+) is also discussed. Dissociative charge exchange of He(+) with H2 is an important source of H(+) in regions of large fractional abundance of H2, as well as an important destruction mechanism for He(+) even for small f (at least 0.1). The calculated molecular abundances are consistent with some of the available observational information.
Glassgold, A. E.↗
Photodissociation processes in the OH molecule
The potential energy curves of several excited states of OH of 2Sigma(+), 2Sigma(-), 2Pi, and 2Delta symmetries, and the transition moments connecting the excited states with the ground state and with each other, are calculated using two previously published theoretical models. The importance of the excited states in photodissociation is explored. Direct photodissociation by absorption into repulsive electronic states, as well as the contribution of absorption into bound electronic states, are discussed. Because they may participate in the photodissociation processes, several quartet states and one of the sextet spin multiplicity are investigated. The mechanism by which bound states can be dissociated are considered and estimates of the dissociation efficiencies of the mechanisms are made. Absorption into the bound 3 2Pi state may be an important dissociation channel. It is shown that OH is dissociated by the absorption of Lyman alpha radiation, a channel of particular significance in shocked interstellar gas and in cometary atmospheres.
Van Dishoeck, E. F.↗