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The mid-infrared spectra of large PAHs ranging from C54H18 to C130H28 are determined computationally using Density Functional Theory. Trends in the band positions and intensities as a function of PAH size, charge and geometry are discussed. Regarding the 3.3, 6.3 and 11.2 micron bands similar conclusions hold as with small PAHs. This does not hold for the other features. The larger PAH cations and anions produce bands at 7.8 micron and, as PAH sizes increases, a band near 8.5 micron becomes prominent and shifts slightly to the red. In addition, the average anion peak falls slightly to the red of the average cation peak. The similarity in behavior of the 7.8 and 8.6 micron bands with the astronomical observations suggests that they arise from large, cationic and anionic PAHs, with the specific peak position and profile reflecting the PAH cation to anion concentration ratio and relative intensities of PAH size. Hence, the broad astronomical 7.7 micron band is produced by a mixture of small and large PAH cations and anions, with small and large PAHs contributing more to the 7.6 and 7.8 micron component respectively. For the CH out-of-plane vibrations, the duo hydrogens couple with the solo vibrations and produce bands that fall at wavelengths slightly different than their counterparts in smaller PAHs. As a consequence, previously deduced PAH structures are altered in favor of more compact and symmetric forms. In addition, the overlap between the duo and trio bands may reproduce the blue-shaded 12.8 micron profile., Comment: ApJ, 36 pages, 9 figs

Over the past few decades, NASA missions have revealed that we live in a Universe that is not a hydrogen-dominated, physicist's paradise, but in a molecular Universe with complex molecules directly interwoven into its fabric. These missions have shown that molecules are an abundant and important component of astronomical objects at all stages of their evolution and that they play a key role in many processes that dominate the structure and evolution of galaxies. Closer to home in our galaxy, the Milky Way, they have revealed a unique and complex organic inventory of regions of star and planet formation that may well represent some of the prebiotic roots to life. Astrobiology emerges from the great interest in understanding astrochemical evolution from simple to complex molecules, especially those with biogenic potential and the roles they may play as primordial seeds in the origin of life on habitable worlds. The first part of this talk will highlight how infrared spectroscopic studies of interstellar space, combined with dedicated laboratory simulations, have revealed the widespread presence of complex organics across deep space. The remainder of the presentation will focus on the evolution of these materials and astrobiology.

Great strides have been made in our understanding of interstellar material thanks to advances in infrared astronomy and laboratory astrophysics. Ionized polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier astrochemical standards, are widespread and very abundant throughout much of the cosmos. In cold molecular clouds, the birthplace of planets and stars, interstellar atoms and molecules freeze onto extremely cold dust and ice particles forming mixed molecular ices dominated by simple species such as water, methanol, ammonia, and carbon monoxide. Within these clouds, and especially in the vicinity of star and planet forming regions, these ices and PAHs are processed by ultraviolet light and cosmic rays forming hundreds of far more complex species, some of biogenic interest. Eventually, these are delivered to primordial planets by comets and meteorites. As these materials are the building blocks of comets and related to carbonaceous micrometeorites, they are likely to be important sources of complex organic materials delivered to habitable planets (including the primordial Earth) and their composition may be related to the origin of life. This talk will focus on the chemical evolution of these cosmic materials and their relevance to astrobiology.

The composition of interstellar ice and dust provides insight into the chemical history of the interstellar medium and early solar system. It is now possible to probe this unique and unusual chemistry and determine the composition of these microscopic interstellar particles which are hundreds to many thousands of light years away thanks to substantial progress in two areas: astronomical spectroscopic techniques in the middle-infrared, the spectral region most diagnostic of chemical composition, and laboratory simulations which realistically reproduce the critical conditions in various interstellar environments. High quality infrared spectra of many different astronomical sources, some associated with giant, dark molecular clouds -the birthplace of stars and planets- and others in more tenuous, UV radiation rich regions are now available. The fundamentals of IR spectroscopy and what comparisons of astronomical IR spectra with laboratory spectra of materials prepared under realistic simulated interstellar conditions tell us about the components of these materials is the subject of this talk. These observations have shown that mixed molecular ices comprised of H2O, CH3OH, CO, NH3 and H2CO contain most of the molecular material in molecular clouds and that gas phase, ionized polycyclic aromatic hydrocarbons (PAHs) are widespread and surprisingly abundant throughout most of the interstellar medium.

In studying various interstellar and solar system ice analogs, we have recently found that upon vacuum ultraviolet photolysis, polycyclic aromatic hydrocarbons (PAHs) frozen in water ice at low temperatures are easily ionized and indefinitely stabilized as trapped ions (Gudipati; Gudipati & Allamandola). Here we report the first experimental study that shows that PAH ionization energy is significantly lowered in PAH/H2O ices, in agreement with recent theoretical work (Woon & Park). The ionization energy (IE) of the PAH studied here, quaterrylene (C40H20, IE = 6.11 eV), is lowered by up to 2.11 eV in water ice. PAH ionization energy reduction in low-temperature water ice substantially expands the astronomical regions in which trapped ions and electrons may be important. This reduction in ionization energy should also hold for other types of trapped species in waterrich interstellar, circumstellar, and solar system ices. Subject headings: ISM: clouds - methods: laboratory - molecular processes - radiation mechanisms: nonthermal -ultraviolet: ISM - ultraviolet: solar system

Over the past fifteen years, thanks to significant, parallel advancements in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role aromatic materials play in the interstellar medium (ISM). Twenty years ago, the possible existence of an abundant population of large, carbon-rich molecules in the ISM was unthinkable. Today, the unmistakable spectroscopic signatures of polycyclic aromatic hydrocarbon molecules (PAHs) - shockingly large molecules by the standards of traditional interstellar chemistry - are recognized throughout the Universe. In this paper, we will examine the current state of the interstellar PAH model and its utility as a diagnostic tool to derive insight into the nature of the interstellar PAH population. As an example of this application, we will examine the results of our recent spectroscopic studies of polycyclic aromatic nitrogen heterocycles (PANHs)-PAHs with an atom of nitrogen substituted into the aromatic skeleton-and discuss a possible tracer of such species amongst the interstellar PAH emission bands in the latest observational data.

In situ ultraviolet-visible absorption and emission studies of vacuum ultraviolet (VUV) irradiated water-rich, cosmic ice analogs containing polycyclic aromatic hydrocarbons (PAHs) are described. W V irradiation of 12 K water ices containing the PAHs naphthalene (H2O/C10H8 = 200) and 4-methylpyrene (H2O/C17H12 > 500) readily converts the PAHs into their cation form (PAH(+)). Under these conditions, PAH photoionization is the predominant reaction. These ions are trapped and stored in the ices at temperatures between 10 and 50 K, a temperature domain common to ices throughout interstellar clouds and the solar system. Unlike the approx.15% ionization typical after W V irradiation of PAHs isolated in rare-gas matrices, in water ice, PAH photoionization and storage proceed efficiently and almost quantitatively with a greater than 70% ionization yield. As the temperature is increased from 50 to 150 K, the PAH ion bands slowly diminish as the PAH ions ultimately react to form more complex organic species involving the water host. The chemical, spectroscopic, and physical properties of these ion-rich ices can be important in icy objects such as molecular clouds, comets, and planets. Several astrophysical applications are presented.

Nitriles are one of the most common classes of molecules observed in the gas phase in space, with over a dozen having been positively identified in interstellar and circumstellar environments through the detection of their rotational transitions. Acids, in contrast, are much less common. In this paper we present laboratory data comparing the stability of two structurally related acid-nitrile pairs to ultraviolet (UV) photolytic destruction: acetic acid vs. acetonitrile (CH3-COOH vs. CH3-CN) and glycine vs. aminoacetonitrile (H2N-CH2-COOH vs. H2N-CH2-CN). We find that the nitriles are destroyed ten and five times more slowly (respectively) by UV photolysis than are the corresponding acids. This suggests that whatever their relative formation rates, acids may be less abundant than nitriles in interstellar environments in part because they are more rapidly destroyed by photolysis. The results of this infrared (IR) spectral matrix isolation study indicate that during the lifetime of a typical interstellar cloud, even in its darkest regions, a population of acids in the gas phase will likely be diminished by at least half. Since aminoacetonitrile is a precursor to the amino acid glycine, and far more stable, presolar aminoacetonitrile may be a contributor to the deuterium enriched glycine detected in meteorites. It would clearly be informative to search for aminoacetonitrile (the nitrile corresponding to glycine) in the regions where the amino acid glycine has been reported.

Water-rich, mixed molecular ices and polycyclic aromatic hydrocarbons (PAHs) are common throughout interstellar molecular clouds and the Solar System. Vacuum ultraviolet (VUV) irradiation and particle bombardment of these abiotic ices produces complex organic species, including important biogenic molecules such as amino acids and functionalized PAHs which may have played a role in the origin of life. This ability of such water-rich, oxygen dominated ices to promote production of complex organic species is surprising and points to an important, unusual, but previously overlooked mechanism at play within the ice. Here we report the nature of this mechanism using electronic spectroscopy. VUV-irradiation of PAH/H2O ices leads to an unprecedented and efficient (greater than 70 %) conversion of the neutral PAHs to their cation form (PAH+). Further, these H2O/PAH+ ices are stabile at temperatures below 50 K, a temperature domain common throughout interstellar clouds and the Solar System. Between 50 and 125 K they react to form the complex organics. In view of this, we conclude that charged PAHs and other molecular ions should be common and abundant in many cosmic ices. The chemical, spectroscopic and physical properties of these ion-rich ices can be of fundamental importance for objects as diverse as comets, planets, and molecular clouds and may account for several poorly understood phenomena associated with each of these object classes.

The cosmic deuterium to hydrogen (D/H) ratio is of key importance from a cosmological and stellar evolution perspective since deuterium originates from big-bang nucleosynthesis and is destroyed by stellar thermonuclear reactions. Further, from the interstellar perspective, the galactic distribution of deuterium and the D/H ratio among various molecular species also traces interstellar chemical evolution. Over the past few decades, radio observations have enabled the study of a handful of small, deuterated interstellar species. However, the number of deuterated species detected and environments probed are limited, raising issues of selection effects that hamper generalization and applications to other environments. Infrared spectroscopy of the interstellar medium offers a distinct advantage in this regard as the extent of deuteration of entire chemical families, rather than one species, can be probed. These observations require spaceborne telescopes because the molecular vibrations involving D which produce the strongest IR bands fall in spectral regions which are obscured by terrestrial CO2 absorption. Here we report the tentative detection of the C-D stretching vibration from deuterated interstellar polycyclic aromatic hydrocarbons in the Orion nebula. Since the PAH emission features are widespread and probe many different types of cosmic environments, follow up observations of deuterated PAHs will provide fundamental, far reaching new insight and perspective into galactic and extragalactic processes.

The gas-phase electronic absorption spectra of the naphthalene (C10H8(+)) and acenaphthene (C12H10(+)) cations have been measured in the visible range in a free 10 jet planar expansion in an attempt to collect data in an astrophysically relevant environment. The direct absorption spectra of two out of four bands measured of the gas-phase cold naphthalene cation along with the gas-phase vibronic absorption spectrum of the cold acenaphthene cation are reported for the first time. The study has been carried out using the ultrasensitive and versatile technique of cavity ringdown spectroscopy (CRDS) coupled to a pulsed discharge slit nozzle (PDN). The new CRDS-PDN set up is described and its characteristics are evaluated. The direct-absorption spectra of the PAH ions are discussed and compared to the gas-phase and solid-phase data available in the literature. The analysis of the results show that cold, free flying PAH ions are generated in the argon discharge primarily through soft Penning ionization. This enables the intrinsic band profiles to be measured, a key requirement for astrophysical applications.

The optical luminescent properties for a variety of vacuum-ultraviolet (VUV) irradiated cosmic ice analogs and the complex organic residues produced from irradiation might be applicable to Solar System and interstellar observations and processes for various astronomical objects with an ice heritage. Some examples include grain temperature determination and vaporization rates, nebula radiation balance, albedo values, color analysis, and biomarker identification. Detailed results are presented for the mixed molecular ice: H2O:CH3OH:NH3:CO (100:50:1:1), a realistic representation for an interstellar/precometary ice. The irradiated ices and the room-temperature residues resulting from this energetic processing have remarkable photoluminescent properties in the visible (520-570 nm). The luminescence dependence on temperature, thermal cycling, and VUV exposure of the residue is described.

Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. ID We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with LTV light from a hydrogen plasma lamp: The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

Infrared spectroscopy in the 2.5-16 micron range is a principle means by which organic compounds can be detected and identified in space via their vibrational transitions. Ground-based, airborne, and spaceborne IR spectral studies have already demonstrated that a significant fraction of the carbon in the interstellar medium (ISM) resides in the form of complex organic molecular species. Furthermore, the presence of D-enriched organics in meteorites suggests that a portion of these materials survives incorporation into protosolar nebulae. Unfortunately, neither the distribution of these materials nor their genetic and evolutionary relationships with each other or their environments are well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corporation. ABE will conduct IR spectroscopic observations to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. The core observational program would make fundamental scientific progress in understanding (1) the evolution of ices and organic matter in dense molecular clouds and young forming stellar systems, (2) the chemical evolution of organic molecules in the ISM as they transition from AGB outflows to planetary nebulae to the general diffuse ISM to HII regions and dense clouds, (3) the distribution of organics in the diffuse ISM, (4) the nature of organics in the Solar System (in comets, asteroids, satellites), and (5) the nature and distribution of organics in local galaxies. In addition, ABE will attempt to detect and quantify deuterium enrichments in a select set of these materials and environments. This should assist both with understanding the chemical processes that occur in these environments and with establishing any links that exist between interstellar and meteoritic organics.

One of the primary tasks of the Astrochemistry Laboratory at Ames Research Center is to use laboratory simulations to study the chemical processes that occur in dense interstellar clouds. Since new stars are formed in these clouds, their materials may be responsible for the delivery of organics to new habitable planets and may play important roles in the origin of life. These clouds are extremely cold (less than 50 kelvin), and most of the volatiles in these clouds are condensed onto dust grains as thin ice mantles. These ices are exposed to cosmic rays and ultraviolet (UV) photons that break chemical bonds and result in the production of complex molecules when the ices are warmed (as they would be when incorporated into a star-forming region). Using cryovacuum systems and UV lamps, this study simulates the conditions of these clouds and studies the resulting chemistry. Some of the areas of progress made in 1999 are described below. It shows some of the types of molecules that may be formed in the interstellar medium. Laboratory simulations have already confirmed that many of these compounds are made under these conditions.

We present 2338-2322 per centimeter (4.277-4.307 micrometer) infrared spectra of a number of N2-containing mixed molecular ices and demonstrate that the strength of the infrared "forbidden" band due to the N=N stretch near 2328 per centimeter (4.295 micrometer) is extremely sensitive to the composition of the ice. The strength of the 2328 per centimeter N2 fundamental is significantly enhanced relative to that of pure N2 ice when NH3, H2O, or CO2 are present, but is largely unaffected by the presence of CO, CH4 or O2. We use the laboratory data in coil junction with ISO data that probes several lines-of-sight through dense molecular clouds to place limits on the abundance of interstellar solid phase N2 and the composition of the ices. Deriving upper limits is complicated by the presence of overlapping absorptions due to CO2 gas in the clouds and, in some cases, to photospheric CO in the background star. These upper limits are just beginning to be low enough to constrain interstellar grain models and the composition of possible N2-bearing interstellar ices. We outline the search criteria that will need to be met if solid interstellar N2 is to be detected in the future. We also discuss some of the implications of the presence of warm CO2 gas along the lines-of-sight to embedded protostars and demonstrate that its presence may help resolve certain puzzles associated with the previously derived gas/solid CO2 ratios and the relative abundances of polar and nonpolar ices towards these objects. Finally, we briefly comment on the possible implications of these results for the interpretation of N2 detections on outer solar system bodies.

To better understand the chemical species that gives rise to the 2165/cm (4.62 micron) "XCN" absorption feature seen towards embedded protostars such as W33A, we have performed laboratory studies using deuterium (H-2) isotopic labeling. We report the observation of a small but significant deuterium isotope shift for the "XCN" peak which demonstrates that the atomic motion(s) causing the "XCN" band in the laboratory samples must involve hydrogen. We also report the results of C-13, N-15 and O-18 labeling experiments that are consistent with previously reported values.

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in two closely related areas: observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at and the notion of abundant, gas phase, polycyclic aromatic hydrocarbons (PAHs) anywhere in the interstellar medium (ISM) considered impossible. Today the dust composition of the diffuse and dense ISM is reasonably well constrained and the spectroscopic case for interstellar PAHs, shockingly large molecules by early interstellar chemistry standards, is very strong.

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to micron-sized cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In dense molecular clouds, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier interstellar chemistry standards, is widespread throughout the Universe. The first part of this lecture will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, concentrations, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the solar nebula during the star and planet formation stage, the materials frozen into interstellar/precometary ices are photoprocessed by ultraviolet light, producing more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the early Earth. As these materials are thought to be the building blocks of comets and related to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex organic materials on the early Earth and their composition may be related to the origin of life.

We report here on our lab studies of ice photochemistry of large organic molecules under cometary conditions. We focus on polycyclic aromatic hydrocarbons (PAHs), their photoproducts, and their similarities to molecules seen in living systems today. We note that these kinds of compounds are seen in meteorites and we propose an explanation for both their formation and their observed deuterium enrichments.

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHs) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For non-adjacent and doubly-adjacent CH groups, the shift is pronounced and consistently toward higher frequencies. The non-adjacent modes are blueshifted by an average of 27 per cm and the doubly-adjacent modes by an average of 17 per cm. For triply- and quadruply-adjacent CH out-of-plane modes the ionization shifts are more erratic and typically more modest. As a result of these ionization shifts, both the non-adjacent and doubly-adjacent CH out-of-plane modes move out of the regions classically associated with their respective vibrations in neutral PAHs. The doubly-adjacent modes of ionized PAHs tend to fall into the frequency range traditionally associated with the non-adjacent modes, while the non-adjacent modes are shifted to frequencies above those normally attributed to out-of-plane bending vibrations. Consequently, the origin of the interstellar infrared emission feature near 11.2 microns, traditionally attributed to the out-of-plane bending of non-adjacent CH groups on PAHs is rendered ambiguous. Instead, this feature likely reflects contributions from both non-adjacent CH units in neutral PAHs and doubly-adjacent CH units in PAH cations, the dominant charge state in the most energetic emission regions. This greatly relieves the structural constraints placed on the interstellar PAH population by the dominance of the 11.2 micron band in this region and eliminates the necessity to invoke extensive dehydrogenation of the emitting species. Furthermore, these results indicate that the emission between 926 and 904 per cm (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the non-adjacent CH out-of-plane bending modes of moderately-sized (fewer than 50 carbon atom) PAH cations making this emission an unequivocal tracer of ionized interstellar PAHs.

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

Laboratory results demonstrate that polycyclic aromatic hydrocarbons (PAHs) rapidly exchange their hydrogen atoms with those of nearby molecules when they are frozen into low-temperature ices and exposed to vacuum ultraviolet radiation. As a result, PAHs quickly become deuterium-enriched when VUV irradiated in D-containing ices. This mechanism has important consequences for several astrophysical issues owing to the ubiquitous nature of PAHs in the interstellar medium. For example, this process may explain the deuterium enrichments found in PAHs in meteorites and interplanetary dust particles. These results also provide general predictions about the molecular siting of the deuterium on aromatic materials in meteorites if this process produced a significant fraction of their D-enrichment.

We present the 2320-2050/cm (4.31-4.88 micron) infrared spectra of 16 solid state nitrites, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C(is congruent to)N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile phenylcyanide) 9-anthracenecarbonitrile, dimethylcyanamide, isopropy1nitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyr-uvonitrile, dicyandiamide, cyanamide, n-butyfisocyanide, methylisocyanoacetate, dilsopropylcarbodiimide, and hydrogen cyanide. The C(is congruent to)N stretching bands of the majority of nitrites fall in the 2300-2200/cm (4.35-4.55 micron) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contest, the isonitriles and a few exceptional nitrites and related species produce bands at lower frequencies spanning the 2200-2080/cm (4.55-4.81 micron) range. These features also have similar positions in both Am and H2O matrices and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C(is congruent to)N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165/cm (4.62 micron) "XCN" interstellar feature and the 4550/cm (2.2 micron) feature of various objects in the solar system are discussed.

The infrared spectra of CO frozen in non-polar ices containing N2, CO2, O2, and H2O, and the ultraviolet photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140/cm (4.673 micrometer) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing non-polar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a very good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices.

The InfraRed (IR) spectra of UltraViolet (UV) and thermally processed, methanol-containing interstellar / cometary ice analogs at temperatures from 12 to 300 K are presented. Infrared spectroscopy, H-1 and C-13 Nuclear Magnetic Resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry indicate that CO (carbon monoxide), CO2 (carbon dioxide), CH4 (methane), HCO (the formyl radical), H2CO (formaldehyde), CH3CH2OH (ethanol), HC([double bond]O)NH2 (formamide), CH3C([double bond]O)NH2 (acetamide), and R[single bond]C[triple bond]N (nitriles) are formed. In addition, the organic materials remaining after photolyzed ice analogs have been warmed to room temperature contain (in rough order of decreasing abundance), (1) hexamethylenetetramine (HMT, C6H12N4), (2) ethers, alcohols, and compounds related to PolyOxyMethylene (POM, ([single bond]CH2O[single bond](sub n)), and (3) ketones (R[single bond]C([double bond]O)[single bond]R') and amides (H2NC([double bond]O)[single bond]R). Most of the carbon in these residues is thought to come from the methanol in the original ice. Deuterium and C-13 isotopic labeling demonstrates that methanol is definitely the source of carbon in HMT. High concentrations of HMT in interstellar and cometary ices could have important astrophysical consequences. The ultraviolet photolysis of HMT frozen in H2O ice readily produces the 'XCN' band observed in the spectra of protostellar objects and laboratory ices, as well as other nitriles. Thus, HMT may be a precursor of XCN and a source of CN in comets and the interstellar medium. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia, formaldehyde, and amino acids. Thus, HMT may be a significant source of prebiogenic compounds on asteroidal parent bodies. A potential mechanism for the radiative formation of HMT in cosmic ices is outlined.

The infrared absorption feature near 2950/ cm (3.4 microns), characteristic of dust in the diffuse interstellar medium (ISM), is attributed to C-H stretching vibrations of aliphatic hydrocarbons. We show here that the strength of the band does not scale linearly with visual extinction everywhere, but instead increases more rapidly for objects near the center of the Galaxy, a behavior that parallels that of the Si-O stretching band due to silicate materials in the diffuse ISM. This implies that the grains responsible for the diffuse medium aliphatic C-H and silicate Si-O stretching bands are different from those responsible for much of the observed visual extinction. It also suggests that the distribution of the carbonaceous component of the diffuse ISM is not uniform throughout the Galaxy, but instead may increase in density toward the center of the Galaxy. The similar behavior of the C-H and Si-O stretching bands suggests that these two components may be coupled, perhaps in the form of silicate-core, organic-mantle grains. Several possible models of the distribution of this material are presented and it is demonstrated that the inner parts of the Galaxy has a carrier density that is 5 to 35 times higher than in the local ISM. Depending on the model used, the density of aliphatic material in the local ISM is found to be about 1 to 2 -CH3 groups /cc and about 2 to 5 -CH2- groups/cc. These densities are consistent with the strengths of the 2955 and 2925/ cm (3.38 and 3.42 microns) subfeatures (due to -CH3 and -CH2- groups, respectively) within the overall 2950/ cm (3.4 microns) band being described by the relations A(sub upsilon)/tau(sub 2925/cm) = 270 +/- 40 and A(sub upsilon)/tau(sub 2925/cm) = 250 +/- 40 in the local diffuse ISM.

It is commonly accepted that constant exposure of comets and ice grains to ultraviolet (UV) radiation causes an organic crust to form on their surface, but the exact molecules that comprise the crust remains a mystery. Based on our lab simulations of interstellar and cometary ices (a paper to be submitted this spring) we believe that Hexamethylenetetramine (HMT) may be a major component of the organic crust on the surface of comets and ice grains. The enclosed paper presents the laboratory infrared spectra and UV photochemistry of HMT under conditions akin to that of the interstellar medium.

In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

A weak infrared absorption feature near 4141 wavenumbers (2.415 micrometers) in the spectrum of WL5, an infrared source in the rho Ophiuchus cloud complex, has been detected. It is attributed to molecular hydrogen created by irradiation and frozen in situ into water-rich ices. A second, broader absorption at 4125 wavenumbers centimeters (2.424 micrometers) is probably due to methanol in the ices. The column densities of frozen molecular hydrogen and methanol are inferred to be about 2.5 x 10(exp 18) and 3.0 x 10(exp 19), respectively. There is about three times more frozen molecular hydrogen than frozen carbon monoxide along this line of sight.

We report the detection of a broad absorption band at 2165/cm in the spectrum of L1551 IRS 5. New laboratory results over the 2200-2100/cm wavenumber interval, performed with realistic interstellar ice analogs, suggest that this feature is due to a CN-containing compound. We will refer to this compound as XCN. We also confirm the presence of frozen CO through absorption bands at 2140/cm and 2135/cm. The relative abundance of solid state CO to frozen H2O is about 0.13 while the abundance of XCN seems comparable to that of frozen CO.

H2 is the most abundant molecule in the universe. We demonstrate that this molecule may be an important component of interstellar and possibly intergalactic ices, both because it can be formed in situ, within the ices, and because gas-phase H2 can freeze out onto dust grains in some astrophysical environments. The condensation-sublimation and infrared spectral properties of ices containing H2 are presented. We show that solid H2 in H2O-rich ices can be detected by an infrared absorption band at 4137/cm (2.417 microns). The surface binding energy of H2 to H2O ice was measured to be Delta-H(s)/k = 555 +/- 35 K. Surface binding energies can be used to calculate the residence times of H2 on grain surfaces as a function of temperature. Some of the implications of these results are considered.

The present evaluation of results from over 120 laboratory experiments relevant to the Trafton et al. (1991) discovery of a 2.1253-micron line in the spectrum of Io demonstrates that this band is produced by neither overtones nor combinations of the fundamental bands of molecules already noted on Io. Since the band's frequency is close to the first overtone of the nu(3) asymmetric stretching mode of CO2, attention is given this molecule's behavior under Io conditions. While pure solid CO2, and CO2 intimately mixed in a matrix of solid SO2 and H2S, generate bands of similar widths, these fall at frequencies lower than the Io band. Attention is given to the possible identification of the Io band with CO2 multimers of 'clusters' on Io.

Laboratory-measured, temperature-dependent sticking efficiencies are presently used to derive the surface-binding energies of CO and CO2 on H2O-rich ices, with a view to determining the condensation and vaporization properties of these systems as well as to the measured energies' implications for both cometary behavior and the evolution of interstellar ices. The molecular volume and the surface binding energies are not found to be necessarily related on the basis of simple nearest-neighbor scaling in surface and bulk sites; this may be due to the physical constraints associated with matrix structure-associated physical constraints, which sometimes dominate the volume-binding energies.

The infrared measurements of comets, the compositional information available from interplanetary dust particles (IDPs), and the recent results of flybys to Comet Halley can help in restricting the nature and composition of cometary dust models (c.f., Proceedings of the 20th ESLAB Symposium on Exploration of Halley's Comet, 1986). Researchers tried to incorporate some of these results into a coherent model to account for the observed cometary infrared emission. The presence of 10 and 3.4 micron features in Comet Halley (c.f. Bregman et al. 1987; Wickramasinghe and Allen 1986) indicated the presence of at least two components in the grain material, namely silicates and some form of amorphous carbon. These two components could reside in separate grains or may be parts of composite particles. Both these cases have been considered (see Krishna Swamy el a. 1988a, 1988b). In the absence of refractive index data for cometary analogs, the authors used the optical constants of olivine-rich lunar material 12009.48 (Perry et al. 1972) for the infrared region and that of alpha:C-H film for amorphous carbon (angus et al. 1986). For the visible region, a value of m = 1.38-0.39i was used for the silicates, and values published by Arakawa et al. (1985) were used for the amorphous carbon. These materials should give a representative behavior of the expected results. The model results were compared to observational data. The strength of the 3.4 micron and 10 micron features relative to the adjacent continuum, as well as the slope of the continuum between 2500 and 1250 cm(exp -1) (4 to 8 microns), were used as criteria for comparison. Model calculations with alpha approx. equals -3.5, and also the size distribution function inferred for Comet Halley, with a mass fraction (X) of silicate to amorphous carbon grains of about 40 to 1 can fit the data. A good match is obtained for the infrared spectra of Comets Halley and West from a 40 to 1 mixture of silicate and amorphous carbon grains with a a(exp -3.5) size distribution function. The results are consistent with compositional constraints provided by interplanetary dust particles (IPDs) and Halley flyby data. The variation of grain temperature with heliocentric distance appears to account for the major changes observed in cometary spectra.

IR spectroscopy has been used to ascertain several parameters associated with CO, H2O, and H2O:CO ices' physical behavior. Since CO is noted to be capable of condensing into H2O-rich ices at temperatures that are twice as high as those required for condensation in pure CO, CO is able to condense onto H2O-rich ice grains at temperatures of up to 50 K. CO's presence in H2O ice modestly enhances the effective volatility of the H2O. Attention is given to the implications of these results for cometary models generally and the question of cometary formation specifically.

The 3-200-micron emission of Comet Halley is characterized theoretically by means of numerical simulations. Models with different populations of refractory dust grains are developed, applying compositional and spectral constraints based on ground-based and spacecraft observations. The results are presented in extensive graphs and discussed in detail. Best agreement between predicted and observed Halley emission is obtained for models with 8-40 times more crystalline silicate grains (by mass) than amorphous carbon grains. For the silicate grains, the predominance of large grains and thin carbonaceous coatings are found to account for the lack of a 10-micron silicate feature and the dark appearance of the comet, respectively.

The application of the matrix isolation technique to interstellar problems is described. Following a brief discussion of the interstellar medium (ISM), three areas are reviewed in which matrix experiments are particularly well suited to contribute the information which is sorely needed to further understanding of the ISM. The first involves the measurement of the spectroscopic properties of reactive species. The second is the determination of reaction rates and the elucidation of reaction pathways involving atoms, radicals, and ions which are likely to interact on grain surfaces and in grain mantles. The third entails the determiantion of the spectroscopic, photochemical, and photophysical properties of interstellar and cometary ice analogs. Significant, but limited, progress has been made in these three areas, and a tremendous amount of work is required to fully address the variety of unique chemical and spectroscopic questions posed by the astronomical observations.

Spectrophotometry from 5 to 9 microns (resolution = 0.02) of comet Halley was obtained from the Kuiper Airborne Observatory on 1985 Dec. 12.1 and 1986 April 8.6 and 10.5 UT. Two spectral features are apparent in all the observations, one from 5.24 to 5.6 microns, and the silicate emission feature which has an onset between 7 and 8 microns. There is no evidence for the 7.5 microns feature observed by the Vega 1 spacecraft; the large difference between the areal coverage viewed from the spacecraft and the airplane may explain the discrepancy. Color temperatures significantly higher than a blackbody indicate that small particles are abundant in the coma. Significant spatial and temporal variations in the spectrum show trends similar to those observed from the ground.

The unidentified infrared (UIR) features are a group of emission bands observed in a variety of objects, which can be characterized as having moderate density gas (densities from 1000 to 1,000,000/cu.cm.) and a nearby ultraviolet source. The origin of the features is still uncertain, but the current evidence points to Polycyclic Aromatic Hydrocarbons (PAHs) as the source of the UIR features. Problems with identifying PAHs as the source of the UIR features are discussed.

The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.

The rate at which the CH bond in interstellar Polycyclic Aromatic Hydrocarbons (PAHs) rupture due to the absorption of a UV photon has been calculated. The results show that small PAHs (less than or equal to 25 carbon atoms) are expected to be partially dehydrogenated in regions with intense UV fields, while large PAHs (greater than or equal to 25 atoms) are expected to be completely hydrogenated in those regions. Because estimate of the carbon content of interstellar PAHs lie in the range of 20 to 25 carbon atoms, dehydrogenation is probably not very important. Because of the absence of other emission features besides the 11.3 micrometer feature in ground-based 8 to 13 micrometer spectra, it has been suggested that interstellar PAHs are partially dehydrogenated. However, IRAS 8 to 22 micrometer spectra of most sources that show strong 7.7 and 11.2 micrometer emission features also show a plateau of emission extending from about 11.3 to 14 micrometer. Like the 11.3 micrometer feature, this new feature is attributed to the CH out of plane bending mode in PAHs. This new feature shows that interstellar PAHs are not as dehydrogenated as estimated from ground-based 8 to 13 micrometer spectra. It also constrains the molecular structure of interstellar PAHs. In particular, it seems that very condensed PAHs, such as coronene and circumcoronene, dominate the interstellar PAH mixture as expected from stability arguments.

The mid-infrared spectrum of a continuously increasing number of stellar objects, planetary and reflection nebulae, H-II regions and extragalactic sources show a distinctive set of broad emission features at 3.3, 3.4, 6.2, 7.7, 8.6, and 11.3 micron known collectively as the unidentified infrared emission bands. A model is summarized in which the bands arise from positively charged polycyclic hydrocarbons (PAH's) on the basis of their low ionization potential and the excellent agreement between the emission bands and laboratory spectra of auto exhaust which contains these types of molecules. The proposed presence of PAHs in such a variety of objects points to their presence in the interstellar medium. Out of a previously published collection of solid state PAH radical cation spectra five were selected on the basis of the unique thermodynamic stability of their carrier and compared directly to the wavelengths of the DIB's. Although the match seems quite favorable, strongly suggesting that PAH radicals are the long sought after carrier of the diffuse interstellar absorption bands, much laboratory work must be done to test this hypothesis.

Interstellar molecular grain mantles are an important component of the interstellar dust inside dense molecular clouds as evidenced by the detection of absorption bands at 2.97, 3.08, 4.61, 6.0 and 6.8 microns. Mantles may also be the precursors of more complex grain mantles in the diffuse interstellar medium. The molecular composition of these icy grain mantles were calculated employing gas phase as well as grain surface reactions. The calculated mixtures consist mainly of the molecules H2O, H2CO, N2, CO, O2, H2O2, NH2, and their deuterated counterparts in varying ratios. The exact compositions depend strongly on the physical conditions in the gas phase. The absorption spectra of H2O with other molecules was studied in the laboratory. Optical constants were determined for a few selected mixtures. Extinction and polarization cross sections across the 3 micron ice band were calculated. A comparison with the observations towards BN shows that the low frequency wing observed on this feature is due to absorption by a mixture of H2O and other molecules rather than scattering by large, pure H2O ice grains.

Techniques for determining the composition of small dust grains in interstellar matter are discussed. The best way to study the composition of interstellar grain mantles is by infrared spectroscopy. The absorption features in a complete infrared spectrum from 2 to 15 microns can be used as fingerprints to identify the absorbing molecule. Ground-based observations around 3 microns confirmed the presence of H2O ice in interstellar grain mantles, through the detection of the 3.08 micron OH stretching vibration. The detection of other molecules, in particular the carbon bearing molecules, is however hampered by atmospheric absorption in the 5-8 micron region and the presence of the strong ice and silicate bands, which dominate the 3 and 10 micron region respectively. Kuiper Airborne Observatory observations of the 5-8 micron region of the spectrum are therefore extremely important to determine the composition of interstellar grain mantles. The 5 to 8 micron spectra of molecular cloud sources was obtained using a 24 detector grating spectrometer. An important characteristic of this spectrometer is that the whole spectrum is obtained simultaneously. It is therefore relatively easy to correct for atmospheric transmission.