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NASA NTRS1989

Infrared fluorescence from PAHs in the laboratory

Several celestial objects, including UV rich regions of planetary and reflection nebulae, stars, H II regions, and extragalactic sources, are characterized by the unidentified infrared emission bands (UIR bands). A few years ago, it was proposed that polycyclic aromatic hydrocarbon species (PAHs) are responsible for most of the UIR bands. This hypothesis is based on a spectrum analysis of the observed features. Comparisons of observed IR spectra with lab absorption spectra of PAHs support the PAH hypothesis. An example spectrum is represented, where the Orion Bar 3.3 micron spectrum is compared with the absorption frequencies of the PAHs Chrysene, Pyrene, and Coronene. The laser excited 3.3 micron emission spectrum is presented from a gas phase PAH (azulen). The infrared fluorescence theory (IRF) is briefly explained, followed by a description of the experimental apparatus, a report of the results, and discussion.

Cherchneff, Isabelle↗

NASA NTRS1989

PAH in the laboratory and interstellar space

The theory that polycyclic aromatic hydrocarbons (PAHs) are a constituent of the interstellar medium, and a source of the IR emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3 microns is being studied using PAH containing acid insoluble residue of the Orgueil CI meteorite and coal tar. FTIR spectra of Orgueil PAH material that has undergone thermal treatment, and a solvent insoluble fraction of coal tar that has been exposed to hydrogen plasma are presented. The UV excided luminescence spectrum of a solvent soluble coal tar film is also shown. Comparison of the lab measurements with observations appears to support the interstellar PAH theory, and shows the process of dehydrogenation expected to take place in the interstellar medium.

Wdowiak, Thomas J.↗

NASA NTRS1989

The effect of ionization on the infrared absorption spectra of PAHs: A preliminary report

The emission lines observed in many interstellar IR sources at 3.28, 6.2, 7.7, 8.7, and 11.3 microns are theorized to originate from polycyclic aromatic hydrocarbons (PAHs). These assignments are based on analyses of lab IR spectra of neutral PAHs. However, it is likely that in the interstellar medium that PAHs are ionized, i.e., are positively charged. Besides, as pointed out by Allamandola et al., although the IR emission band spectrum resembles what one might expect from a mixture of PAHs, it does not match in details such as frequency, band profile, or relative intensities predicted from the absorption spectra of any known PAH molecule. One source of more information to test the PAH theory is ab initio molecular orbital theory. It can be used to compute, from first principles, the geometries, vibrational frequencies, and vibrational intensities for model PAH compounds which are difficult to study in the lab. The Gaussian 86 computer program was used to determine the effect of ionization on the infrared absorption spectra of several small PAHs: naphthalene and anthracene. A preliminary report is presented of the results of these calculations.

Defrees, Doug J.↗

NASA NTRS1989

Angular motion of a PAH molecule in interstellar environment

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Rouan, D.↗

NASA NTRS1989

Molecules, grains, and shocks: A comparison of CO, H I, and IRAS data

The IR and H I properties, and CO content were compared for a set of 26 isolated, degree-sized interstellar clouds. The comparisons offer some conclusions concerning the effects of kinematics on molecular content and grain size distribution. It was also found that some clouds must have very large fractions of their total Carbon in the form of polycyclic aromatic hydrocarbons.

Heiles, Carl↗

NASA NTRS1989

Properties of grains derived from IRAS observations of dust

The authors used the results of Infrared Astronomy Satellite (IRAS) observations of diffuse medium dust to develop a theoretical model of the infrared properties of grains. Recent models based entirely on traditional observations of extinction and polarization include only particles whose equilibrium temperatures do not exceed 20 K in the diffuse interstellar medium. These classical grains, for which the authors have adopted the multipopulation model developed by Hong and Greenberg (1980), can explain only the emission in the IRAS 100 micron band. The measurements at shorter wavelengths (12, 25 and 60 microns) require two new particle populations. Vibrational fluorescence from aromatic molecules provides the most likely explanation for the emission observed at 12 microns, with polycyclic aeromatic hydrocarbons (PAHs) containing about 10 percent of cosmic carbon. A simplified model of the emission process shows that PAH molecules can also explain most of the emission measured by IRAS at 25 microns. The authors identified the warm particles responsible for the excess 60 microns emission with small (a approx. equals 0.01 microns) iron grains. A compilation of the available data on the optical properties of iron indicates that the diffuse medium temperature of small iron particles should be close to 50 K and implies that a large, possibly dominant, fraction of cosmic iron must be locked up in metallic particles in order to match the observed 60 microns intensities. The model matches the infrared fluxes typically observed by IRAS in the diffuse medium and can also reproduce the infrared surface brightness distribution in individual clouds. In particular, the combination of iron and classical cool grains can explain the surprising observations of the 60/100 microns flux ratio in clouds, which is either constant or increases slightly towards higher opacities. The presence of metallic grains has significant implications for the physics of the interstellar medium, including catalytic H2 formation, for which iron grains could be the main site; differences in depletion patterns between iron and other refractory elements (Mg, Si); and superparamagnetic behavior of large grains with embedded iron clusters giving rise to the observed high degree of alignment by the galactic magnetic field.

Wesselius, P. R.↗

NASA NTRS1989

The pre- and post-accretion irradiation history of cometary ices

Comets Halley and Wilson exhibited similar 3.4 micron emission features at approx. 1 AU from the Sun. A simple model of thermal emission from organic grains fits the feature, provides optical depths in good agreement with spacecraft measurements, and explains the absence of longer-wavelength organic features as due to spectral heliocentric evolution (Chyba and Sagan, 1987). The model utilizes transmission spectra of organics synthesized in the laboratory by irradiation of candidate cometary ices; the authors have long noted that related gas-phase syntheses yield polycyclic aromatic hydrocarbons, among other organic residues (Sagan et al., 1967). The authors previously concluded (Chyba and Sagan, 1987) that Halley's loss of several meters' depth with each perihelion passage, combined with the good fit of the Halley 3.4 micron feature to that of comet Wilson (Allen and Wickramasinghe, 1987), argues for the primordial - but not necessarily interstellar - origin of cometary organics. The authors examine the relative importance to the formation of organics of the variety of radiation environments experienced by comets. They conclude that there is at present no compelling reason to choose any of three contributing mechanisms (pre-accretion UV, pre-accretion cosmic ray, and post-accretion radionuclide processing) as the most important.

Chyba, Christopher↗

NASA NTRS1989

PAH formation in carbon-rich circumstellar envelopes

While there is growing observational evidence that some fraction of interstellar carbon is in polycyclic aromatic hydrocarbons (PAH's), the mechanisms by which these molecules might be formed have not been extensively studied. A detailed investigation of PAH production in the outflowing molecular envelopes of carbon-rich red giant star is presented. The gasphase kinetics of a chemical reaction mechanism developed to study soot production in hydrocarbon flames is modified to apply in circumstellar environments. It was found that astrophysically significant quantities of PAH's can be formed in carbon star envelopes provided the gas is sufficiently dense and resides for a long time in the temperature range of 900 to 1100 k. The precise yield of PAH's is very sensitive to astronomical parameters of the envelope (e.g., mass loss rate, outflow velocity, and acetylene abundance) and certain poorly determined chemical reaction rates.

Feigelson, Eric D.↗

NASA NTRS1990

Characterization of a thermally imidized soluble polyimide film

A soluble aromatic poly(amic acid) film was converted to a soluble polyimide by staging at 25 deg intervals to 325 C and characterized at each interval by several analytical methods. The behavior observed was consistent with an interpretation that a reduction occurred in molecular weight of the poly(amic acid) during the initial stages of cure before the ultimate molecular weight was achieved as a polyimide. This interpretation was supported by the results of solution viscosity, gel permeation chromatography, low angle laser light scattering photometry and infrared spectroscopy analysis. The results serve to increase the fundamental understanding of how polyimides are thermally formed from poly(amic acids).

Young, Philip R.↗

NASA NTRS1990

Association reactions at low pressure. III - The C2H2(+)/C2H2 system

An ion cyclotron resonance mass spectrometer is used to examine the association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2, at pressures in the range of 8 x 10 to the -8 to 1 x 10 to the -4 Torr at 298 K. The association of C4H2(+) and C4H3(+) with C2H2 was found to exhibit classical behavior in the pressure range of 5 x 10 to the -8 Torr to 0.4 Torr. It is found that an efficient route via radiative association exists for unsaturated hydrocarbon cations to convert to aromatic structures in the presence of acetylene.

Anicich, Vincent G.↗

NASA NTRS1991

Size and density distribution of very small dust grains in the Barnard 5 cloud

The effects of the temperature fluctuations in small graphite grains on the energy spectrum and the IR surface brightness of an isolated dust cloud heated externally by the interstellar radiation field were investigated using a series of models based on a radiation transport computer code. This code treats self-consistently the thermal coupling between the transient heating of very small dust grains and the equilibrium heating of conventional large grains. The model results were compared with the IRAS observations of the Barnard 5 (B5) cloud, showing that the 25-micron emission of the cloud must be produced by small grains with a 6-10 A radius, which also contribute about 50 percent to the observed 12-micron emission. The remaining 12 micron flux may be produced by the polycyclic aromatic hydrocarbons. The 60-and 100-micron radiation is dominated by emission from large grains heated under equilibrium conditions.

Lis, Dariusz C.↗

NASA NTRS1990

High temperature polymers - A review of novel thermally stable hexafluoroisopropylidene-containing polymers

The synthesis and properties to date of several novel HFIP-containing polymers and copolymers are presented. Thermal analyses of polyether ketones (PEK), aromatic polyesters, and polymers from a novel 18F-diacid were performed on a thermal analyzer. All three polymer types exhibited enhanced solubility, thermal stability, and low dielectric constants that are predicted for polymers containing the HFIP moiety. The moderate thermal stability observed in the polymers derived from the 18F-diacid is attributed to the oxidatively weak methylene linkage between the HFIP groups and the phenyl rings. PEKs and polyarylates show potential as high emissivity coatings under conditions where atomic oxygen is present.

Kane, K. M.↗

NASA NTRS1990

Synthesis and characterization of polyamide-imides

The synthesis and characterization of polyamide-imides (PAI) derived from four different dianhydrides and three isomers of diaminobenzanilide are discussed with emphasis on the effect of combining an amide linkage in the diamine portion with other bridging groups in the dianhydride portion of the polymer backbone. It is noted that all of the amide-imide polymers exhibit high-glass transition temperatures, high thermooxidative stability, and a relatively good solvent resistance. These aromatic PAIs are characterized by high thermal stability due to chain stiffness, crystallinity, and intermolecular hydrogen bonding, and are considered to be good candidates as high-temperature films, coatings, and fibers for aerospace applications.

Dezern, James F.↗

NASA NTRS1991

The role of matrix material and CCl4 (electron acceptor) on the ionization mechanisms of matrix-isolated naphthalene

The formation mechanisms and optical properties of polycyclic aromatic hydrocarbons (PAH) isolated in argon and neon matrices were studied in a systematic manner in an attempt to provide spectroscopic data on PAH ions under conditions relevant to astrophysical applications. The results obtained indicate the strong influence of the matrix material on the competing radiative (fluorescence and phosphorescence) and nonradiative (internal conversion and intersystem crossing) relaxation processes of the trapped molecule.

Salama, F.↗

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 NTRS1991

Isotopic constraints on the origin of meteoritic organic matter

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement isotopic correlation should also be revealed, which will aid in identifying pertinent synthetic processes.

Kerridge, J. F.↗

NASA NTRS1991

Preparation of atomic oxygen resistant polymeric materials

Polyphenyl quinoxalines (PPQs) are an important family of high performance polymers that offer good chemical and thermal stability coupled with excellent mechanical properties. These aromatic heterocyclic polymers are potentially useful as films, coatings, adhesives, and composite materials that demand stability in harsh environments. Our approach was to prepare PPQs with pendent siloxane groups using the appropriate chemistry and then evaluate these polymers before and after exposure to simulated atomic oxygen. Either monomer, the bis(o-diamine)s or the bis(alpha-diketone)s can be synthesized with a hydroxy group to which the siloxane chain will be attached. Several novel materials were prepared.

Tortorelli, Victor J.↗

NASA NTRS1991

Structure-property study of keto-ether polyimides

As part of an on-going effort to develop an understanding of how changes in the chemical structure affect polymer properties, an empirical study was performed on polyimides containing only ether and/or carbonyl connecting groups in the polymer backbone. During the past two decades the structure-property relationships in linear aromatic polyimides have been extensively investigated. More recently, work has been performed to study the effect of isomeric attachment of keto-ether polyimides on properties such as glass transition temperature and solubility. However, little work has been reported on the relation of polyimide structure to mechanical properties. The purpose of this study was to determine the effect of structural changes in the backbone of keto-ether polyimides on their mechanical properties, specifically, unoriented thin film tensile properties. This study was conducted in two stages. The purpose of the initial stage was to examine the physical and mechanical properties of a representative group (four) of polyimide systems to determine the optimum solvent and cure cycle requirements. These optimum conditions were then utilized in the second stage to prepare films of keto-ether polyimides which were evaluated for mechanical and physical properties. All of the polyimides were prepared using isomers of oxydianiline (ODA) and diaminobenzophenone (DABP) in combination with 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-oxydiphthalic anhydride (ODPA).

Dezern, James F.↗