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At least 289 records · Page 16

Synthesis, Characterization and Decomposition Studies of Tris(N,N-dibenzyldithiocarbamato) Indium(III): Chemical Spray Deposition of Polycrystalline CuInS2 on Copper Films

Tris(bis(phenylmethyl)carbamodithioato-S,S ), commonly referred to as tris(N,Ndibenzyldithiocarbamato) indium(III), In(S2CNBz2)3, was synthesized and characterized by single crystal X-ray crystallography. The compound crystallizes in the triclinic space group P1 bar with two molecules per unit cell. The material was further characterized using a novel analytical system employing the combined powers of thermogravimetric analysis, gas chromatography/mass spectrometry and Fourier-Transform infrared spectroscopy to investigate its potential use as a precursor for the chemical vapor deposition (CVD) of thin film materials for photovoltaic applications. Upon heating, the material thermally decomposes to release CS2 and benzyl moieties in to the gas phase, resulting in bulk In2S3. Preliminary spray CVD experiments indicate that In(S2CNBz2)3 decomposed on a Cu substrate reacts to produce stoichiometric CuInS2 films.

Hehemann, David G.↗

Trace Gas Measurements in Nascent, Aged and Cloud-processed Smoke from Africa Savanna Fires by Airborne Fourier Transform Infrared Spectroscopy (AFTIR)

We measured stable and reactive trace gases with an airborne Fourier transform infrared spectrometer (AFTIR) on the University of Washington Convair-580 research aircraft in August/September 2000 during the SAFARI 2000 dry season campaign in Southern Africa. The measurements included vertical profiles of C02, CO, H20, and CH4 up to 5.5 km on six occasions above instrumented ground sites and below the TERRA satellite and ER-2 high-flying research aircraft. We also measured the trace gas emissions from 10 African savanna fires. Five of these fires featured extensive ground-based fuel characterization, and two were in the humid savanna ecosystem that accounts for most African biomass burning. The major constituents we detected in nascent CH3OOH, HCHO, CH30H, HCN, NH3, HCOOH, and C2H2. These are the first quantitative measurements of the initial emissions of oxygenated volatile organic compounds (OVOC), NH3, and HCN from African savanna fires. On average, we measured 5.3 g/kg of OVOC and 3.6 g/kg of hydrocarbons (including CH4) in the initial emissions from the fires. Thus, the OVOC will have profound, largely unexplored effects on tropical tropospheric chemistry. The HCN emission factor was only weakly dependent on fire type; the average value (0.53 g/kg) is about 20 times that of a previous recommendation. HCN may be useful as a tracer for savanna fires. Delta O3/Delta CO and Delta CH3COO/Delta CO increased to as much as 9% in <1 h of photochemical processing downwind of fires. Direct measurements showed that cloud processing of smoke greatly reduced CH30H, NH3, CH3COOH, SO2, and NO2 levels, but significantly increased HCHO and NO.

Yokelson, Robert J.↗

The bulk motion of gas in the core of the Centaurus galaxy cluster

Galaxy clusters contain vast amounts of hot ionized gas known as the intracluster medium (ICM). In relaxed cluster cores, the radiative cooling time of the ICM is shorter than the age of the cluster. However, the absence of line emission associated with cooling suggests heating mechanisms that offset the cooling, with feedback from active galactic nuclei (AGNs) being the most likely source. Turbulence and bulk motions, such as the oscillating (‘sloshing’) motion of the core gas in the cluster potential well, have also been proposed as mechanisms for heat distribution from the outside of the core. Here we present X-ray spectroscopic observations of the Centaurus galaxy cluster with the X-Ray Imaging and Spectroscopy Mission satellite. We find that the hot gas flows along the line of sight relative to the central galaxy, with velocities from 130 km s −1 to 310 km s −1 within about 30 kpc of the centre. This indicates bulk flow consistent with core gas sloshing. Although the bulk flow may prevent excessive accumulation of cooled gas at the centre, it could distribute the heat injected by the AGN and bring in thermal energy from the surrounding ICM. The velocity dispersion of the gas is found to be only ≲120 km s −1 in the core, even within about 10 kpc of the AGN. This suggests that the influence of the AGN on the surrounding ICM motion is limited in the cluster.

galaxies and clusters↗

Evidence for large-scale winds from starburst galaxies. I - The nature of the ionized gas in M82 and NGC 253

The results of long-slit spectroscopy and narrow-band imaging of M82 and NGC 253, the two nearest examples of FIR luminous galaxies believed to be undergoing intense bursts of star formation, are presented. The profile of the gas pressure in the emission-line filaments in M82 is derived and found to be in good agreement with the model of Chevalier and Clegg (1985) of a supernovae-driven wind from a starburst nucleus. Lower quality data from NGC 253 support the same interpretation. Analysis of the emission-line ratios suggests that the line-emitting gas may be heated by low-velocity shocks, although photoionization from dilute UV radiation from unusually hot stars in the central starburst may also be important.

Mccarthy, Patrick J.↗

Portable Multigas Monitors for International Space Station

The Environmental Health System (EHS) on International Space Station (ISS) includes portable instruments to measure various cabin gases that acutely impact crew health. These hand-held devices measure oxygen, carbon dioxide, carbon monoxide, hydrogen chloride and hydrogen cyanide. The oxygen and carbon dioxide units also serve to back up key functions of the Major Constituent Analyzers. Wherever possible, commercial off-the-shelf (COTS) devices are employed by EHS to save development and sustaining costs. COTS hardware designed for general terrestrial applications however has limitations such as no pressure compensation, limited life of the active sensor, calibration drift, battery issues, unpredictable vendor support and obsolescence. The EHS fleet (inflight and ground inventory) of instruments is both aging and dwindling in number. With the retirement of the US Space Shuttle, maintenance of on-orbit equipment becomes all the more difficult. A project is underway to search for gas monitoring technology that is highly reliable and stable for years. Tunable Diode Laser Spectroscopy (TDLS) seems to be the front-runner technology, but generally is not yet commercially available in portable form. NASA has fostered the development of TDLS through the Small Business Innovative Research (SBIR) program. A number of gases of interest to the aerospace and submarine communities can be addressed by TDLS including the list mentioned above plus hydrogen fluoride, ammonia and water (humidity). There are several different forms of TDLS including photoacoustic and direct absorption spectroscopy using various multipass cell geometries. This paper describes the history of portable gas monitoring on NASA spacecraft and provides a status of the development of TDLS based instruments. Planned TDLS flight experiments on ISS could lead both to operational use on ISS and important roles in future Exploration spacecraft and habitats.

Mudgett, Paul D.↗

Probing Noncovalent Interaction Strengths of Host-Guest Complexes Using Negative Ion Photoelectron Spectroscopy

Noncovalent interactions (NCIs) are crucial for the formation and stability of host-guest complexes, which have wide-ranging implications across various fields, including biology, chemistry, materials science, pharmaceuticals, and environmental science. However, since NCIs are relatively weak and sensitive to bulk perturbation, direct and accurate measurement of their absolute strength has always been a significant challenge. This concept article aims to demonstrate the gas-phase electrospray ionization (ESI)-negative ion photoelectron spectroscopy (NIPES) as a direct and precise technique to measure the absolute interaction strength, probe nature of NCIs, and reveal the electronic structural information for host-guest complexes. Here, our recent studies in investigating various host-guest complexes that involve various types of NCIs such as anion–π, (di)hydrogen bonding, charge-separated ionic interactions, are overviewed. Finally, a summary and outlook are provided for this field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-Equilibrium in a Dust-Forming Low-Temperature Plasma: A CARS Study

Dust-forming low-temperature plasmas are versatile systems for the production of nanoparticles with tunable functionalities. While attractive from a materials processing point of view, these systems are inherently complex, with several plasma-induced phenomena determining the properties of the produced materials. Here, we characterize a carbon nanoparticle-forming plasma using coherent anti-Stokes Raman spectroscopy (CARS), with the primary goal of measuring gas temperature. While gas temperature is typically assumed to be at or slightly above room temperature in these reactors, we measure gas temperatures exceeding 1000 K under typical process conditions. We find a correlation between the gas temperature and the nanoparticle yield, suggesting that the particle nucleation and growth process releases energy within the reaction volume, leading to significant gas heating. In addition, we find that the relaxation of vibrationally excited species at the particle surfaces is a major contributor to their heating. In conclusion, these results underscore the complexity of these systems and the need for their more in-depth characterization using advanced techniques such as CARS.

Basic Plasma Phenomena and Gas Discharges↗

Black Hole Demographics in and Nuclear Properties of Nearby Low Luminosity Radio Galaxies; Connections to Radio Activity?

We combine the results of an HST STIS and WFPC study of a complete sample of 21 nearby UGC low luminosity radio galaxies with the results of a radio VLA and VLBA study of the same sample. We examine the relationship between the stellar and gaseous properties of the galaxies on tens to hundreds of parsec scale with the properties of the radio jets on the same scale. From the VLA and VLBA data we constrain the physics of the outflowing radio plasma from the tens of parsecs to hundreds of kiloparsec scales. From the WFPC2 H alpha and dust images and the STIS kinematics of the near nuclear gas we obtain constraints on the orientation of near nuclear disks of gas and measures of the nuclear stellar, continuum point source, and line emission fluxes. Under the statistically supported assumption that the radio jet issues perpendicular to the disk, we use the orientation of the optical (large scale accretion?) disks to constrain the three-dimensional orientation of the radio ejection. From HST/STIS spectroscopy of the near-nuclear emission line gas we obtain measures/limits on the black hole masses. We examine correlations between the VLBA and VLA-scale radio emission, the nuclear line emission, and the nuclear optical and radio continuum emission. Though our sample is relatively small, it is uniquely well defined, spans a narrow range in redshift and we have a consistent set of high resolution data with which to carefully examine these relationships. We use the combined radio and optical data to: 1) Constrain the orientation, physics, and bulk outflow speed of the radio plasma; 2) Put limits on the mass accretion rate and study the relationship between black hole mass, radio luminosity, and near nuclear gaseous content; 3) Provide insight into the relationship between BL Lac objects and low luminosity radio galaxies.

Baum, S. A.↗

Real-time measurements of endogenous CO production from vascular cells using an ultrasensitive laser sensor

Carbon monoxide (CO) has been implicated as a biological messenger molecule analogous to nitric oxide. A compact gas sensor based on a midinfrared laser absorption spectroscopy was developed for direct and real-time measurement of trace levels (in approximate pmol) of CO release by vascular cells. The midinfrared light is generated by difference frequency mixing of two nearinfrared lasers in a nonlinear optical crystal. A strong infrared absorption line of CO (4.61 microm) is chosen for convenient CO detection without interference from other gas species. The generation of CO from cultured vascular smooth muscle cells was detected every 20 s without any chemical modification to the CO. The sensitivity of the sensor reached 6.9 pmol CO. CO synthesis was measured from untreated control cells (0.25 nmol per 10(7) cells/h), sodium nitroprusside-treated cells (0.29 nmol per 10(7) cells/h), and hemin-treated cells (0.49 nmol per 10(7) cells/h). The sensor also detected decreases in CO production after the addition of the heme oxygenase (HO) inhibitor tin protoporphyrin-IX (from 0.49 to 0.02 nmol per 10(7) cells/h) and increases after the administration of the HO substrate hemin (from 0.27 to 0.64 nmol per 10(7) cells/h). These results demonstrate that midinfrared laser absorption spectroscopy is a useful technique for the noninvasive and real-time detection of trace levels of CO from biological tissues.

Non-NASA Center↗

Cerium Dimer Anion and the Contribution of 4f Electrons to Lanthanide Metal–Metal Bonds

Direct metal−metal bonding between lanthanide atoms has been challenging to observe. We report on the first spectroscopic characterization of the cerium dimer anion (Ce 2 − ) and its neutral analog (Ce 2 ) in the gas phase, achieved using photoelectron and ultrafast spectroscopy combined with high-level quantum chemistry calculations. The electron affinity of Ce 2 is 0.24 eV, from which a dissociation energy of 2.21 eV is derived for Ce 2 − . The wave-packet dynamics upon photodetachment are studied and yield vibrational frequencies for electronically excited Ce 2 . Ce 2 − exhibits a conventional metal−metal triple bond with minimal contribution from 4f electrons. However, evidence of 4f-electron participation in bonding is identified for the low-energy excited states only 0.1 eV higher. The results challenge the assumption of inert 4f electrons in metal−metal bonding, and we propose a promising strategy for forming stable lanthanide−lanthanide bonds involving significant 4f-electron contributions.

Anions↗

Modern insights into the mechanisms of neptunium oxalate decomposition

Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗

Study of carbon compounds in Apollo 12 and 14 lunar samples.

The results of gas-chromatography and high-resolution mass spectroscopy studies of gases released on deuterium fluoride dissolution of Apollo 12 and 14 lunar samples are reported. The results confirm previous observations that CH4 and C2H6 are released as well as CD4, C2D4, C2D6, and higher deuterated hydrocarbons. The yields correlate with the total carbon content of the samples, and the CH4 and C2H6 released may be regarded as indigenous, while the deuterated products result from hydrolysis of carbide material. The results provide the first experimental confirmation of the hypothesis that the CH4 derives from solar wind interactions.

Holland, P. T.↗

Determining total carbon in hydrazine

Procedure incorporates modified pyrolysis train. Samples are vaporized before entering furnace to be pyrolyzed at 850 C + or - 25 C. Direct collection of pyrolyzed gas reduces loss of carbon dioxide. Infrared spectroscopy can be used to analyze samples for carbon dioxide content.

Davis, E. E.↗

Prospects for cosmic X-ray spectroscopy

Attention is given to solar X-ray spectroscopy, the determination of the ionization of gas and geometrical distribution of gas in binary X-ray sources, and the investigation of extragalactic X-ray sources. The HEAO-B satellite which carries a focusing X-ray telescope with three powerful spectrometers is considered.

Mccray, R.↗

Ultraviolet spectroscopy of comets

Results of observations of comets in the ultraviolet are reviewed in relation to their significance for the chemistry and physics of the cometary coma and the composition of the cometary ice. Ultraviolet cometary observations began in 1970, when a hydrogen envelope was discovered extending millions of kilometers from the nucleus of comet Bennett, and continued with the discovery of oxygen and carbon in comet Kohoutek and the acquisition of comprehensive UV spectra from comets West (1976 VI), Seargent (1978 XV) and Bradfield (1979 X). The available cometary spectra are remarkably similar, indicative of a common composition and origin for comets and the insignificance of chemical reactions in the inner coma to species abundances. Ultraviolet spectroscopy has also allowed the determination of gas production rates from either the surface brightness or the total luminosity in a given spectral line. IUE observations of comet Bradfield reveal the water production rate to vary as the -3.7 power of heliocentric distance from 0.71 to 1.55 AU, incompatible with solar energy input as the controlling influence on water vaporization.

Feldman, P. D.↗

Synthesis and thermal stability of carborane containing phosphazenes

Carborane substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl penta chlorocyclotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring chain equilibrium processes of decomposition.

Fewell, L. L.↗

Synthesis and thermal stability of carborane-containing phosphazenes

Carborane-substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl pentachlorocylotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. Previously announced in STAR as A83-21034

Fewell, L. L.↗