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NASA NTRS1989

High resolution spectroscopy of the 11.3 micron emission band

High resolution spectra of the 11.3 micron emission band in M82 and NGC 7027 were obtained using the University of Texas IR echelle spectrometer on the IRTF in April 1988. The spectral resolution was 0.004 micron, with coverage from 11.0 to 11.6 microns. Spectra were measured at ten positions along a 10 min. long slit. Analysis of the data is still in progress, but initial results show no clear evidence of narrow structure within the feature. The analysis will involve comparison of the observed spectra to laboratory and predicted spectra of Polycylic Aromatic Hydrocarbons (PAHs) and Quenched Carbonaceous Composite (QCCs) to determine which may be responsible for the emission. The spectra will be examined with a goal of determining whether the emission is caused by molecular or solid state material. The data are also examined for evidence of variations in the shape and strength of the 11.3 micron feature with position on the sky. In NGC 7027 the 10 min. long slit went across the edge of the ionized nebulae, allowing comparison of emission from both ionized and neutral regions.

Achtermann, Jeff M.↗
NASA NTRS1989

Spatial variations of the 3 micron emission features within nebulae

The 3 micron spectra is presented for the Orion bar region and the Red Rectangle. In both objects spectra were obtained at more than one location, corresponding to different distances from the excitation source. The well known 3.3 and 3.4 micron emission bands are seen in both objects as well as the recently discovered features at 3.46, 3.51, and 3.57 microns in the Orion bar spectra. The spectra show that the relative strengths of the 3 micron emission features vary within the Orion bar. As distance from the exciting star increases, the 3.4 and 3.51 micron features increase, and the 3.46 micron feature decreases in strength, relative to the strong 3.3 micron feature. These are two possible interpretations which are postulated, each of which involves the breaking of bonds by UV radiation, which removes the modes responsible for the 3.4 micron emission near the star. The two possible bond ruptures are the CH bond in small polycyclic aromatic hydrocarbons (PAHs), or the bond to an aliphatic subgroup. It has to be pointed out that neither interpretation appears entirely satisfactory. The vibrational overtone interpretation cannot explain the presence or behavior of the 3.46 micron feature, whereas the laboratory spectra of aliphatic sidegroups contain many more features in the 3 micron region than are observed in the astronomical sources.

Moorhouse, Alan↗
NASA NTRS1989

Red fluorescence and 3-12 micron emission in NGC 2023, HD 44179, M 82, and Lynds 1780

A red excess observed in the Red Rectangle (HD 44179), was attributed to a possible molecular fluorescence mechanism was discovered in NGC 2023 and analyzed in subsequent work in this and other nebulae. An unexpected red light excess was also noticed in a high latitude dark cloud L 1780. The fluorescence was attributed to hydrogenated amorphous carbon by Duley (1985), on the basis of laboratory work. Alternatively, transitions between electronic states of free polycyclic aromatic hydrocarbon molecules, by-passing the cascade along the vibrational states was considered. In L 1780, the red excess was related to the 12 micron emission detected by IRAS. A quantitative comparison of the intensity of the red fluorescence and that of the 3 to 12 micron features is thus warranted in helping assess the physical properties of large interstellar molecules. The red fluorescence radiation, F(R), appears as a bump on the spectra between 0.6 and 0.9 micron. Values were deduced from the spectra for HD 44179, and for the high latitude cloud L 1780. Corrections for the extinction, both interstellar and internal to the nebulae, were included. The 3 to 12 micron brightness, F(IR), was obtained through integration of the spectra for NGC 2023, and for HD 44179 after removal of a smooth continuum due to hot large grains. The values of the ratio of fluorescence flux to the infrared flux, F(R)/F(IR), are summarized. Red fluorescence and infrared radiation are two separate ways to access to the size of the molecules through observation, and it is rewarding that both approaches give similar results. These findings bring a striking coherence into the physical description of the particles, and add further support to the initial attribution of the infrared features to polycyclic aromatic hydrocarbons (PAHs).

Ryter, Charles↗
NASA NTRS1989

The spatial distribution of infrared radiation from visible reflection nebulae

The emission at IRAS 12 and 25 micron bands of reflection nebulae is far in excess of that expected from the longer wavelength equilibrium thermal emission. The excess emission in the IRAS 12 micron band is a general phenomenon, seen in various components of interstellar medium such as IR cirrus clouds, H II regions, atomic and molecular clouds, and also normal spiral galaxies. This excess emission has been attributed to UV excited fluorescence in polycyclic aromatic hydrocarbon (PAH) molecules or to the effect of temperature fluctuations in very small grains. Results are presented of studies of IRAS data on reflection nebulae selected from the van den Bergh reflection nebulae sample. Detailed scans of flux ratio and color temperature across the nebulae were obtained in order to study the spatial distribution of IR emission. A model was used to predict the spatial distribution of IR emission from dust grains illuminated by a B type star. The model was also used to explore the excitation of the IRAS 12 micron band emission as a function of stellar temperature. The model predictions are in good agreement with the analysis of reflection nebulae, illuminated by stars with stellar temperature ranging from 21,000 down to 3,000 K.

Luan, Ling↗
NASA NTRS1989

Influence of temperature on the infrared spectrum of the coronene molecule

Laboratory experiments were performed to study the temperature dependence of the absorption spectrum of the coronene molecule (C24H12), believed to be representative of the polycyclic aromatic hydrocarbon (PAH) molecules present in the interstellar medium. The main results is that both line positions and total intensities are almost unchanged when varying the temperature so that the spectrum is mostly temperature independent in the explored range, supporting the modeling of the IR emission originally made by Leger and Puget where room temperature was used in the calculations. In the structure of the band shape, small temperature correlated changes are observed. Qualitative arguments are given to interpret them.

Bernard, Jean-Phillipe↗
NASA NTRS1989

Raman properties of various carbonaceous materials and their astrophysical implications

It is well known that a large number of celestial objects exhibit, in the range 3 to 12 micron, a family of emission features called unidentified infrared bands (UIR). They usually appear together and are associated with UV sources. Recently various authors have suggested that these features could be attributed to solid carbonaceous materials. Following this interest, a systematic analysis was performed of various types of amorphous carbon grains and polycyclic aromatic hydrocarbons (PAH), produced in lab. Updating results of Raman measurements performed on several carbonaceous materials, chosen according to their astrophysical interest, are presented. The measurements were made by means of a Jobin-Yvon monochromator HG2S and standard DC electronic. The line at 5145 A of an Ar+ laser was used as excitation source.

Blanco, A.↗
NASA NTRS1991

X-ray irradiation of interstellar grains in active galaxies - Evaporation and infrared spectra

A fundamental physical study of grains heated transiently by X-rays is presented. The X-ray photoionization cross sections used to determine the rate of energy deposition into the grains are given. A grain model is constructed and the radiative and evaporative responses of grains into X-ray absorption are described. The basic theory of stochastic grain heating is outlined, and analytical expressions for the temperature distributions of flickering grains are provided. The resulting IR spectra due to X-ray illumination are given, and the relevance of the present work to the IR continua of active galaxies is discussed. The present model provides two observational predictions: the infrared spectra of grains, even if they are superheated, should show a cutoff between 1 and 3 microns; and X-ray-illuminated environments should exhibit no PAH emissions.

Voit, G. M.↗
NASA NTRS1991

Measurement of the spectral signature of small carbon clusters at near and far infrared wavelengths

A significant percentage of the carbon inventory of the circumstellar and interstellar media may be in the form of large refractory molecules (or small grains) referred to as carbon clusters. At the small end, uneven numbers of carbon atoms seem to be preferred, whereas above 12 atoms, clusters containing an even number of carbon atoms appear to be preferred in laboratory chemistry. In the lab, the cluster C-60 appears to be a particularly stable form and has been nicknamed Bucky Balls because of its resemblance to a soccer ball and to geodesic domes designed by Buckminster Fuller. In order to investigate the prevalence of these clusters, and their relationship to the polycyclic aromatic hydrocarbons (PAHs) that have become the newest focus of IR astronomy, it is necessary to determine the spectroscopic characteristics of these clusters at near and far infrared wavelengths. Described here is the construction of a near to far IR laser magnetic resonance spectrometer that has been built at the University of California Berkeley in order to detect and characterize these spectra. The equipment produces carbon clusters by laser evaporation of a graphitic target. The clusters are then cooled in a supersonic expansion beam in order to simulate conditions in the interstellar medium (ISM). The expansion beam feeds into the spectrometer chamber and permits concentrations of clusters sufficiently high as to permit ultra-high resolution spectroscopy at near and far IR wavelengths. The first successful demonstration of this apparatus occurred last year when the laboratory studies permitted the observational detection of C-5 in the stellar outflow surrounding IRC+10216 in the near-IR. Current efforts focus on reducing the temperature of the supersonic expansion beam that transport the C clusters evaporated from a graphite target into the spectrometer down to temperatures as low as 1 K.

Tarter, J.↗
NASA NTRS1992

Electron energy loss spectra of polycyclic aromatic hydrocarbons

A survey of the electron energy-loss spectroscopy is reported of gas-phase polycyclic aromatic hydrocarbon (PAH) molecules consisting of up to seven rings where the study is limited to the more thermodynamically stable pericondensed systems. The aim of this work is to obtain absorption profiles (proportional to the oscillator strengths) from the visible to the soft X-ray region near 30 eV.

Keller, John W.↗
NASA NTRS1992

Modification of primordial ices by cosmic rays as simulated by cyclotron irradiation

Frozen CH4 and CH4/Ar mixtures closed into metal cuvettes and open to the vacuum were irradiated at 15 and 77 K with 10 - 20 MeV p and He-3(2+) ions in order to simulate the effect of cosmic rays on solid organic matter in space. Ices exposed to vacuum represent surfaces of icy systems whereas closed systems stand for bulk ices. The products were analyzed by MS, SEM, RBS, ERDA, H-1-NMR, HPLC, GC-MS, NEXAFS, and FT-IR. Volatile products consisted of a mixture of low molecular species, e.g., C2H2, C2H4, C2H6, and long linear aliphatic and olefinic compounds. The formation of polycyclic aromatic hydrocarbons (PAH's) and related species in solid CH4 is due to a multi-center reaction within one collision cascade and is governed by energy density effects with critical linear energy transfer values L(sub T) between 2 and 10 keV/micron. Open ices exhibit preferential hydrogen release resulting in an increased carbonization as compared to more hydrogen rich molecules protected inside large icy bodies.

Kaiser, R. I.↗
NASA NTRS1993

Hypervelocity impact survivability experiments for carbonaceous impactors

We performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, fullerenes, phthalic acid crystals, and Murchison meteorite) into Al plate at velocities between 4.2 and 6.1 km/s. These tests were made to do the following: (1) determine the survivability of carbon forms and organize molecules in low hypervelocity impact; (2) characterize carbonaceous impactor residues; and (3) determine whether or not fullerenes could form from carbonaceous impactors, under our experimental conditions, or survive as impactors. An analytical protocol of field emission SEM imagery, SEM-EDX, laser Raman spectroscopy, single and 2-stage laser mass spectrometry, and laser induced fluorescence (LIF) found the following: (1) diamonds did not survive impact at 4.8 km/s, but were transformed into various forms of disordered graphite; (2) intact, well-ordered graphite impactors did survive impact at 5.9 km/sec, but were only found in the crater bottom centers; the degree of impact-induced disorder in the graphite increases outward (walls, rims, ejecta); (3) phthalic acid crystals were destroyed on impact (at 4.2 km/s, although a large proportion of phthalic acid molecules did survive impact); (4) fullerenes did not form as products of carbonaceous impactors (5.9 - 6.1 km/s, fullerene impactor molecules mostly survived impact at 5.9 km/s; and (5) two Murchison meteorite samples (launched at 4.8 and 5.9 km/s) show preservation of some higher mass polycyclic aromatic hydrocarbons (PAHs) compared with the non-impacted sample. Each impactor type shows unique impactor residue morphologies produced at a given impact velocity. An expanded methodology is presented to announce relatively new analytical techniques together with innovative modifications to other methods that can be used to characterize small impact residues in LDEF craters, in addition to other acquired extraterrestrial samples.

Bunch, T. E.↗
NASA NTRS1993

Infrared emission from hydrogenated amorphous carbon and amorphous carbon grains in the interstellar medium

The correlations deduced by Boulanger et al. (1990) from IRAS maps of the Chamaeleon, Taurus and Ursa Major molecular cloud complexes are interpreted in terms of the evolutionary hydrogenated amorphous carbon model of interstellar dust. In particular, regions of relatively strong 12-micron emission may be regions where recently accreted carbon is being converted by ambient UV to small PAHs in situ. Regions of weak 12-micron emission are probably quiescent regions where carbon has been annealed to amorphous carbon. Observational consequences of these inferences are briefly described.

Duley, W. W.↗
NASA NTRS1992

Laboratory spectra of gas-phase coronene at elevated temperatures

Gas-phase infrared spectra of coronene from 4000 to 400/cm are presented in emission and absorption at temperatures from 350 to 450 C. Peak positions are compared to KBr pellet data and to a previously published neon matrix-isolated coronene spectrum. Relative feature strengths are analyzed and used to estimate a temperature of interstellar PAHs assuming thermal emission.

Kurtz, J.↗
NASA NTRS1993

Comment on 'Summary and implications of reported amino acid concentrations in the Murchison meteorite' by E. L. Shock and M. D. Schulte

A criticism of the claim by Shock and Schulte (1990) that there is a correlation between the amino acid abundances (relative to glycine) in the Murchison meteorite and their aqueous solubilities is presented. Their suggestion that 'the same factors which control the aqueous solubility of many amino acids also control their relative abundances in the Murchison meteorite is argued to be incorrect. It is proposed that even though the water/meteorite ratio would have been less during meteorite aqueous alteration than that in the 100-C laboratory extraction procedure, amino acids are simply too soluble. The distribution of other meteorite organic components such as PAHs may have been affected by alteration because they are only slightly soluble in water and can be easily separated by geochromatographic processes. In their reply Shock and Schulte contend that the critics argue against a point not made in their paper and that their argument was supported with several unsubstantiated assertions, including an unfounded claim that the temperature dependence of amino acid solubilities are 'not greatly different', a misrepresentation of isopiestic studies on concentration solutions as equilibrium solubility measurements.

Miller, Stanley L.↗
NASA NTRS1993

Molecular equilibria and condensation sequences in carbon rich gases

Chemical equilibria in stellar atmospheres have been investigated by many authors. Lattimer, Schramm, and Grossman presented calculations in both O rich and C rich environments and predicted possible presolar condensates. A recent paper by Cherchneff and Barker considered a C rich composition with PAH's included in the calculations. However, the condensation sequences of C bearing species have not been investigated in detail. In a carbon rich gas surrounding an AGB star, it is often assumed that graphite (or diamond) condenses out before TiC and SiC. However, Lattimer et al. found some conditions under which TiC condenses before graphite. We have performed molecular equilibrium calculations to establish the stability fields of C(s), TiC(s), and SiC(s) and other high temperature phases under conditions of different pressures and C/O. The preserved presolar interstellar dust grains so far discovered in meteorites are graphite, diamond, SiC, TiC, and possibly Al2O3.

Sharp, C. M.↗
NASA NTRS1994

The peculiar behaviour of the 5780 and 5797 DIBs in HD25137

The interstellar environment close to the high latitude molecular cloud Lynds 1569 (L1569, Lynds 1962), also known as MBM 18 (Magnani, Blitz and Mundy, 1985), has been analyzed by Penrase et al. (1990) and Penrase (1993). Their observations of the CH, CH(sup+), and CN molecular features, are consistent with a region having a high molecular and reduced dust content. They also observed the background star HD 24263- located 8 degrees far from the center of L1569 - reporting a CH rich line of sight and the presence of two intervening clouds from a sodium lines spectra. The infrared excess which has been revealed by the IRAS survey at 12 microns might suggest the presence of PAH's molecules, the well know candidate for the Unidentified Infrared Bands and Diffuse Interstellar Bands. This interesting scenario led to the investigation of the behavior of the diffuse interstellar bands toward HD 25137, which is supposed to be a background object for L1569 (Penrase et al., 1990); as well as the field star HD 24263. As part of a wider observational program devoted to study the HLC's special environments, the observations of the diffuse interstellar bands (DIB's) at 5780 and 5797 lambda lambda in the direction of the two above mentioned stars, HD 24263 and HD 25137 are presented here.

Porceddu, Ignazio↗
NASA NTRS1994

The formation of small grains in shocks in the ISM

Carbonaceous and silicate grains swept up, and betatron accelerated, by supernova-generated shock waves in the interstellar medium are exposed to grain destructive processing. The degree of grain destruction is determined by the differential gas-grain and grain-grain velocities, which lead to sputtering of the grain surface and grain core disruption (deformation, vaporization and shattering), respectively. The threshold pressure for grain shattering in grain-grain collisions (100 k bar) is considerably lower than that for vaporization (approximately 5 M bar). Therefore, collisions between grains shatter large grains into smaller fragments (i.e., small grains and PAH's). Using a new algorithms for the destructive processes, it was possible to model the formation fo small grain fragments in grain-grain collisions in the warm phase of the interstellar medium. It was found that in one cycle through the warm medium (approximately 3 x 10(sup 6) years) of order 1-2% of the total grain mass is shattered into particles with radii of less than 50 A.

Jones, Anthony P.↗
NASA NTRS1995

Direct analysis of organic priority pollutants by IMS

Many routine methods for monitoring of trace amounts of atmospheric organic pollutants consist of several steps. Typical steps are: (1) collection of the air sample; (2) trapping of organics from the sample; (3) extraction of the trapped organics; and (4) identification of the organics in the extract by GC (gas chromatography), HPLC (High Performance Liquid Chromatography), or MS (Mass Spectrometry). These methods are often cumbersome and time consuming. A simple and fast method for monitoring atmospheric organics using an IMS (Ion Mobility Spectrometer) is proposed. This method has a short sampling time and does not require extraction of the organics since the sample is placed directly in the IMS. The purpose of this study was to determine the responses in the IMS to organic 'priority pollutants'. Priority pollutants including representative polycyclic aromatic hydrocarbons (PAHs), phthalates, phenols, chlorinated pesticides, and polychlorinated biphenyls (PCB's) were analyzed in both the positive and negative detection mode at ambient atmospheric pressure. Detection mode and amount detected are presented.

Giam, C. S.↗