Molecular abundances in the magellanic clouds .1. A multiline study of five cloud cores

Nine H II regions of the LMC were mapped in (CO)-C-13(1-0) and three in (CO)-C-12(1-0) to study the physical properties of the interstellar medium in the Magellanic Clouds. For N113 the molecular core is found to have a peak position which differs from that of the associated H II region by 20 ''. Toward this molecular core the (CO)-C-12 and (CO)-C-13 peak T-MB line temperatures of 7.3 K and 1.2 K are the highest so far found in the Magellanic Clouds. The molecular concentrations associated with N113, N44BC, N159HW, and N214DE in the LMC and LIRS 36 in the SMC were investigated in a variety of molecular species to study the chemical properties of the interstellar medium. I(HCO+)/I(HCN) and I(HCN)/I(HNC) intensity ratios as well as lower limits to the I((CO)-C-13)/I((CO)-O-18) ratio were derived for the rotational 1-0 transitions. Generally, HCO+ is stronger than HCN, and HCN is stronger than HNC. The high relative HCO+ intensities are consistent with a high ionization flux from supernovae remnants and young stars, possibly coupled with a large extent of the HCO+ emission region. The bulk of the HCN arises from relatively compact dense cloud cores. Warm or shocked gas enhances HCN relative to HNC. From chemical model calculations it is predicted that I(HCN)/I(HNC) close to one should be obtained with higher angular resolution (less than or similar to 30 '') toward the cloud cores. Comparing virial masses with those obtained from the integrated CO intensity provides an H-2 mass-to-CO luminosity conversion factor of 1.8 x 10(20) mol cm(-2) (K km s(-1))(-1) for N113 and 2.4 x 10(20) mol cm(-2) (K km s(-1))(-1) for N44BC. This is consistent with values derived for the Galactic disk.

The chemistry of deuterium in hot molecular cores

This paper presents the results of a model of the chemistry of deuterium-bearing molecules in hot molecular cores. It is found that because hydrogen- and deuterium-bearing molecules are destroyed by the same reactions at about the same rates, the initial fractionation present in ice mantles persists for over 10(4) yr. This is the case for a wide range of physical conditions, so it is safe to infer the fractionation on grain surfaces from observations of deuterated molecules in hot cores. The implications of the observed abundances of deuterium-bearing species in Orion are then discussed.

DENSE GAS IN NEARBY GALAXIES .9. A SURVEY FOR HNC

Ten detections and five tentative detections of hydrogen isocyanide (HNC) J=1-0 emission are reported from a survey including sixteen galaxies. Full maps are presented for the nuclear regions of NGC 253 and IC 342, partial maps for Maffei 2, M 82, and M 83. Toward IC 342, the HNC and HCO+ distributions differ from those observed in 12CO, 13CO, HCN, CS, and NH3. This is likely a consequence of the density structure. Relative HNC abundances are with 10(-10)-10(-9) much smaller than those measured in nearby dark clouds and appear to be slightly smaller than those in regions of massive star formation of the Galactic disk. This is consistent with the presence of dense warm gas or a frequent occurrence of shocks in the nuclear regions of the galaxies observed. As in prominent Galactic star forming regions, 3 mm HNC line emission tends to be weaker than the corresponding emission from HCN and HCO+. Toward Arp 220, however, the 3 mm HNC/HCN line intensity ratio is > 1. HNC/HCO+, HNC/CO, and HNC to 20 cm radio continuum luminosity ratios are also particularly large. A possible interpretation is the presence of cool quiescent gas outside the central region which contains the starburst. In the other ultraluminous galaxy observed, NGC 6240, X(HNC) 10 smaller than in Arp 220, demonstrating that the molecular composition in ultraluminous galaxies is far from being uniform.

THE CHEMISTRY OF PHOSPHORUS IN HOT MOLECULAR CORES

Hot molecular cores in star-forming regions are known to have gas-phase chemical compositions determined by the material evaporated from the icy mantles of interstellar grains, followed by subsequent reactions in the gas phase. Current models suggest that the evaporated material is rich in hydrogenated species. In this paper, we consider the chemistry induced in a hot core by the release of phosphine, PH3 from interstellar grains. We find that PH3 is rapidly destroyed by a series of reactions with atomic hydrogen and is converted, within 10(4) yr, into atomic P, and PO and PN, with P atoms being the most abundant species. Other P-bearing molecules can be formed in the hot gas, but on time-scales that are long compared to those of the hot cores.

A time-resolved spectroscopy study of the resonance-line emission in the Ge XXIII XUV laser

A comparison is presented of the temporally resolved resonance-line emission from the Ne-like Ge XUV laser (pumped with nanosecond pulses) with the predictions for the same emission from the hydro-atomic code EHYBRID. The specific lines chosen were the two 3s-2p Ne-like lines at 10.01 and 9.762 Angstrom, and the 3s-2p F-like group of lines in the 9.4-9.6 Angstrom region. Modification of the code to include 112 excited levels of the F-like ion facilitated a direct comparison between experiment and model of (i) the temporal variation of the emissions and (ii) the variation of the peak intensity ratios of the F-like to Ne-like emissions with irradiance on target.

Negative ion enhancement in caesium-seeded hydrogen discharges - a volume or surface effect?

Measurements of plasma parameters, including H- ion densities, made in conjunction with wall temperature, visible and vacuum ultraviolet emission spectroscopy verify that there is little caesium in the plasma volume of the H- ion source. Surface work function measurements indicate that there is significant caesium coverage of the inner walls of the ion source. It is found that, as the work function of a test surface decreases due to caesium seeding, the H- ion fraction in the discharge volume increases. These observations combine to indicate that, in the present source, the H- ion enhancement mechanism is a surface dominated effect. (C) 1999 American Institute of Physics. [S0003- 6951(99)04744-0].

ABSORPTION AND EMISSION-SPECTRA OF THE YBCO LASER PLUME

The plasma produced during laser ablation deposition of thin film YBCO has been studied by optical emission spectroscopy. There is evidence of increased YO band emission in the range 590-625 nm as the ambient oxygen gas pressure confining the plume is increased in the range 30-200 m Torr. Temporal profiles show that close to the target the plume is insensitive to ambient oxygen pressure. It is deduced that the optical emission here is excited by electron impact excitation. Further away from the target there is evidence that two distinct processes are at work. One is again electron excitation; the emission from this process decreases with distance because the expanding plume cools and collisions become less frequent in the expanding gas. The second is driven by oxidation of atomic species expelled at high speeds from the target. The main region of this activity is in the plume sheath where a shock front ensures heating of ambient O2 and reaction of monatomic plasma species to form oxide in an exothermic reaction. Spatial mapping of the emission demonstrates clearly how increasing oxygen gas pressure confines the plasma and enhances the emission intensity from the molecular YO species ejected from the target in a smaller region close to the target. Ba+ is observed as a dominant species only very close to (within 1 mm of) the target. Absorption spectra have been taken in an attempt to examine ground state and cool species in the plume. They reveal the quite surprising result that YO persists in the chamber for periods up to 1 msec. This suggests an explanation for the recent report of off-axis laser deposition in terms of simple condensation. Previously, quasi-ballistic transfer of material from target to substrate has been considered the only significant process.

EMISSION STUDIES OF THE PLUME PRODUCED DURING YBA2CU3O7 FILM PRODUCTION BY LASER-ABLATION

The optical plume emissions produced on excimer laser ablation of a YBa2Cu3O7 target are reported and identified with the various atomic, ionic, and molecular species present. The spatial and temporal distribution of these emissions were studied as a function of the laser fluence and oxygen pressure. At the laser fluences used (4-6 J/cm(2)) some target material is ablated or evaporated directly in molecular form. In addition efficient formation of molecular oxides is observed at the contact front of the expanding plume with the surrounding oxygen atmosphere. The intensity and spatial distribution of oxide emission in the visible plume therefore provides a sensitive diagnostic for optimization of substrate location and deposition conditions.

Partial and total multiphoton detachment rates for H- in a perturbative B-spline-based approach

An ab initio approach has been applied to study multiphoton detachment rates for the negative hydrogen ion in the lowest nonvanishing order of perturbation theory. The approach is based on the use of B splines allowing an accurate treatment of the electronic repulsion. Total detachment rates have been determined for two- to six-photon processes as well as partial rates for detachment into the different final symmetries. It is shown that B-spline expansions can yield accurate continuum and bound-state wave functions in a very simple manner. The calculated total rates for two- and three-photon detachment are in good agreement with other perturbative calculations. For more than three-photon detachment little information has been available before now. While the total cross sections show little structure, a fair amount of structure is predicted in the partial cross sections. In the two-photon process, it is shown that the detached electrons mainly have s character. For four- and six-photon processes, the contribution from the d channel is the most important. For three- and five-photon processes p electrons dominate the electron emission spectrum. Detachment rates for s and p electrons show minima as a function of photon energy. © 1994 The American Physical Society.

The electrical characterization and response to hydrogen of Schottky diodes with a resistive metal electrode—rectifying an oversight in Schottky diode investigation

Schottky-barrier structures with a resistive metal electrode are examined using the 4-point probe method where the probes are connected to the metal electrode only. The observation of a significant decrease in resistance with increasing temperature (over a range of similar to 100 K) in the diode resistance-temperature (R(D)-T) characteristic is considered due to charge carrier confinement to the metal electrode at low temperature (high resistance), with the semiconductor progressively opening up as a parallel current carrying channel (low resistance) with increasing temperature due to increasing thermionic emission across the barrier. A simple model is constructed, based on thermionic emission at quasi-zero bias, that generates good fits to the experimental data. The negative differential resistance (NDR) region in the R(D)-T characteristic is a general effect and is demonstrated across a broad temperature range for a variety of Schottky structures grown on Si-, GaAs- and InP-substrates. In addition the NDR effect is harnessed in micro-scaled Pd/n-InP devices for the detection of low levels of hydrogen in an ambient atmosphere of nitrogen.

Selective Hydrogenation of alpha,beta-Unsaturated Aldehydes and Ketones using Novel Manganese Oxide and Platinum Supported on Manganese Oxide Octahedral Molecular Sieves as Catalysts

The selective hydrogenation of ,-unsaturated aldehydes and ketones has been studied using ketoisophorone and cinnamaldehyde as model substrates using manganese oxide octahedral molecular sieve (OMS-2) based catalysts. For the first time, OMS-2 has been shown to be an efficient and selective hydrogenation catalyst. High selectivities for either the CC or CO double bond at approximate to 100% conversion were achieved by using OMS-2 and platinum supported on OMS-2 catalysts. Density functional theory (DFT) calculations showed that the dissociation of H2 on OMS-2 was water assisted and occurred on the surface Mn of OMS-2(001) that had been modified by an adsorbed H2O molecule. The theoretically calculated activation barrier was in good agreement with the experimentally determined value for the hydrogenation reactions, indicating that H2 dissociation on OMS-2 is likely to be the rate-determining step. A significant increase in the rate of reaction was observed in the presence of Pt as a result of the enhancement of H2 dissociative adsorption and subsequent reaction on the Pt or spillover of the hydrogen to the OMS-2 support. The relative adsorption strengths of ketoisophorone and cinnamaldehyde on the OMS-2 support compared with the Pt were found to determine the product selectivity.

Exchange potential from the common energy denominator approximation for the Kohn-Sham Green's function: Application to (hyper)polarizabilities of molecular chains

An approximate Kohn-Sham (KS) exchange potential v(xsigma)(CEDA) is developed, based on the common energy denominator approximation (CEDA) for the static orbital Green's function, which preserves the essential structure of the density response function. v(xsigma)(CEDA) is an explicit functional of the occupied KS orbitals, which has the Slater v(Ssigma) and response v(respsigma)(CEDA) potentials as its components. The latter exhibits the characteristic step structure with "diagonal" contributions from the orbital densities \psi(isigma)\(2), as well as "off-diagonal" ones from the occupied-occupied orbital products psi(isigma)psi(j(not equal1)sigma). Comparison of the results of atomic and molecular ground-state CEDA calculations with those of the Krieger-Li-Iafrate (KLI), exact exchange (EXX), and Hartree-Fock (HF) methods show, that both KLI and CEDA potentials can be considered as very good analytical "closure approximations" to the exact KS exchange potential. The total CEDA and KLI energies nearly coincide with the EXX ones and the corresponding orbital energies epsilon(isigma) are rather close to each other for the light atoms and small molecules considered. The CEDA, KLI, EXX-epsilon(isigma) values provide the qualitatively correct order of ionizations and they give an estimate of VIPs comparable to that of the HF Koopmans' theorem. However, the additional off-diagonal orbital structure of v(xsigma)(CEDA) appears to be essential for the calculated response properties of molecular chains. KLI already considerably improves the calculated (hyper)polarizabilities of the prototype hydrogen chains H-n over local density approximation (LDA) and standard generalized gradient approximations (GGAs), while the CEDA results are definitely an improvement over the KLI ones. The reasons of this success are the specific orbital structures of the CEDA and KLI response potentials, which produce in an external field an ultranonlocal field-counteracting exchange potential. (C) 2002 American Institute of Physics.

Adsorption properties of HKUST-1 toward hydrogen and other small molecules monitored by IR

Among microporous systems metal organic frameworks are considered promising materials for molecular adsorption. In this contribution infrared spectroscopy is successfully applied to highlight the positive role played by coordinatively unsaturated Cu2+ ions in HKUST-1, acting as specific interaction sites. A properly activated material, obtained after solvent removal, is characterized by a high fraction of coordinatively unsaturated Cu2+ ions acting as preferential adsorption sites that show specific activities towards some of the most common gaseous species (NO, CO2, CO, N-2 and H-2). From a temperature dependent IR study, it has been estimated that the H-2 adsorption energy is as high as 10 kJ mol(-1). A very complex spectral evolution has been observed upon lowering the temperature. A further peculiarity of this material is the fact that it promotes ortho-para conversion of the adsorbed H-2 species.