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Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N(2)-, CH(4)-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple ices dominated by N(2), electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ~ 0.9 and O/C ~ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.

The aromatic nitrogen heterocyclic compound purine is the core structural framework of many important biomolecules, particularly nucleobases. Purine and purine derivatives have been observed in carbonaceous chondrites, and it has been hypothesized that the exogenous delivery of these compounds, along with many other biologically relevant compounds, may have played a role in the emergence of life. Numerous experiments in our laboratory have demonstrated that the nucleobases used by life to encode genetic material could have been produced abiotically under astrophysically relevant conditions. Specifically, the UV photoprocessing of pyrimidine and purine in simple ices of astrophysical interest has resulted in the production of all five biological nucleobases, namely, uracil (RNA), cytosine (RNA and DNA), thymine (DNA), adenine (RNA and DNA), and guanine (RNA and DNA). Additionally, follow-up work has examined the photochemistry of pyrimidine in more complex astrophysical ice mixtures to better understand the formation of these compounds under realistic conditions. In this work, we examine the photochemistry of purine in more complex ices of astrophysical interest and compare our results with those from simpler ice mixtures. We also examine the effects of competing parallel synthesis of organic compounds in the ices (unrelated to purine). Finally, we discuss the astrophysical and astrobiological implications of our findings.

Polycyclic aromatic hydrocarbons (PAHs) are generally believed to be ubiquitous in space and responsible for numerous telltale interstellar infrared emission bands. In Sandford et al., we suggested that PAHs with excess hydrogenation at their periphery (-PAHs) may be an important subclass of these molecules in some astrophysical environments. These molecules are candidates to explain objects with anomalously large 3.4 μm features, which are presumed to be associated with the aliphatic C–H stretching vibrations of the excess hydrogen. In that work, we suggest that for Hn-PAHs to be a viable candidate as the source for this 3.4 μm feature, we must also expect to observe methylene scissoring modes at 6.9 μm. In this work, we continue to develop the hypothesis with a focus on the 6.9 μm feature. We also present some new observations of three post-asymptotic giant branch (post-AGB) objects with abnormally large 3.4 μm features, IRAS 04296+3429, IRAS 05341+0852, and IRAS 22272+5435, in addition to one post-AGB object with normal PAH emissions, IRAS 20000+3239. These observations were made using the FORCAST instrument in grism mode on the Stratospheric Observatory for Infrared Astronomy aircraft and demonstrate the presence of a 6.9 μm feature for the three objects with abnormally large 3.4 μm features and no detectable 6.9 μm feature for the normal PAH emitter. These results are consistent with the hypothesis that Hn-PAHs are a possible source of these infrared emission bands.

Using new laboratory spectra, we have calculated the real and imaginary parts of the index of refraction of amorphous and crystalline H2O-ice from 20-150 K in the wavelength range 2.5-22 μm (4000-455 cm–1) and joined these results with previous measurement from 1.25 to 2.5 μm. These optical constants improve on previous measurements by having better temperature and spectral resolution and can be used to create model spectra for comparison to spectra of solar system objects and interstellar materials. In this wavelength range, the infrared band shapes and positions of amorphous H2O-ice are strongly dependent on deposition temperature. Amorphous and crystalline H2O-ice have distinctive spectral bands at all wavelengths in this region with bands weakening and shifting to shorter wavelength in amorphous H2O-ice compared to crystalline H2O-ice. Some notable exceptions are the band near 6 μm, which is stronger in amorphous H2O-ice, and the bands near 4.5 μm and 12.5 μm, which shift to longer wavelength in amorphous H2O-ice.

Polycyclic aromatic hydrocarbons (PAHs) have been observed in absorption along lines of sight toward embedded protostars. In such cold space environments PAHs should condense into H2O-rich ice mantles at low temperature and be exposed to ionizing radiation. In this paper we present the first infrared spectra of PAH cations in solid H2O generated under conditions that resemble dense molecular clouds. After exposing PAHs in solid H2O at 15 K to low doses of UV radiation, we have observed both the vibrational absorptions of PAH cations in the mid-IR and electronic transitions in the near-IR. The PAHs observed as ions in solid H2O were naphthalene, anthracene, phenanthrene, benzo[k]fluoranthene, and benzo[ghi]perylene. Peak positions, strengths, and temperature dependence are reported for the detected ion bands, and their astrophysical significance is discussed. These laboratory measurements suggest that absorption bands of PAH cations in H2O ice may be observable by astronomers in the near- and mid-infrared.

Amino acids have been identified in carbonaceous chondrites, but their origin is yet unknown. Previous work has shown that a variety of amino acids can be formed via ultraviolet photolysis of interstellar ice analogs. Two possible mechanisms of formation of these amino acids have been proposed: a Strecker-type synthesis or a radical-radical mechanism. In this work, we have used isotopic labeling techniques to test the predictions made by each of these proposed mechanisms for the formation of the amino acids glycine and serine. We observe that amino acid formation occurs via multiple pathways, with potentially different mechanisms for glycine and serine. The major reaction paths do not match either of the two predicted mechanisms, although a modified radical-radical mechanism may account for our observations. The observation of multiple routes suggests that the formation of amino acids in interstellar ice analogs is not narrowly dependent on ice composition, but may occur under a variety of conditions that influence product distributions.

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe. Their detection and identification are based on telescopic infrared (IR) spectra compared with laboratory data. Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics i.e., PAHs with carbon atoms replaced by a nitrogen atom. These molecules should be present in the interstellar medium, but have received relatively little attention. We present mid-IR spectra of two PANHs, quinoline (C9H7N), and phenanthridine (C13H9N) isolated in solid argon and frozen in solid H2O at 12 K, conditions yielding data directly comparable to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H2O. Whereas the IR spectrum of phenanthridine in H2O is similar to that of the same compound isolated in an argon matrix, quinoline absorptions shift up to 16 cm(sup -1) (0.072 mm) between argon and H2O. Thus, astronomers will not always be able to rely on IR band positions of matrix isolated PANHs to correctly interpret the absorptions of PANHs frozen in H2O ice grains. Furthermore, our data suggest that relative band areas also vary, so determining column densities to better than a factor of 3 will require knowledge of the matrix in which the PANH is embedded and laboratory studies of relevant samples.

In this paper, we present the results of a computational study of the effects of a low absolute level of deuteration (~5%) on the observed mid-IR spectrum of the interstellar polycyclic aromatic hydrocarbon (PAH) population. The analyses are based on a global average spectrum, including all the possible singly deuterated isomers of an ensemble of partially superhydrogenated PAH species (i.e., Hn-PAHs) in both neutral and cationic forms. The distinctive spectroscopic properties considered in this paper include three classes of D-involved vibrational modes: (1) C–D in-plane bending features in the 9.5-12 μm region, (2) C–D out-of-plane bending features in the 14.5-17.9 μm region, and (3) aromatic and aliphatic C–D stretching features in the 4.4-4.7 μm region. In addition, D substitution also has the potential to alter the appearance of the C–H out-of-plane bending features in the 11-14 μm region by disrupting the adjacency of the H atoms on the PAH edge rings. The spectroscopic impacts of a low level of deuteration in the interstellar PAH population are considered, and their implications for the detailed appearance of the astronomical mid-IR PAH emission spectrum is explored. Overall, the results of this study indicate that the C–D stretching features offer the greatest prospects for the detection of deuterated interstellar PAHs. Since these features are effectively obscured by telluric CO2 absorptions, the information presented herein should be useful in the planning and design of future space-based IR observing platforms.

Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe. Gas-phase PAHs are easily detected in radiation-rich environments by the characteristic infrared (IR) emission bands they produce when they are excited by higher energy radiation. In contrast, in dense interstellar clouds, where the PAHs could be present as unexcited gas-phase molecules or dust grains or frozen into ice mantles, they are expected to be seen in absorption. We present full mid-IR spectra of the PAH naphthalene (C10H8) in several media to facilitate searches for PAHs in absorption in dense clouds. The positions, widths, and strengths of the absorption bands of naphthalene are significantly altered from the gas phase when it is placed in a matrix, with the extent of the alteration depending on the nature of the matrix interaction. The infrared features of gas-phase naphthalene show P, Q, and R branches characteristic of rovibrational transitions, while naphthalene in condensed forms does not. When condensed in a relatively inert matrix (e.g., Ar or N2), the IR features produced by naphthalene are narrow (generally FWHM < 2 cm-1) and may show multiple components associated with different matrix sites. In more interactive matrices (e.g., pure naphthalene and H2O), the bands become considerably broader (factors of 3-10), show small band position shifts (0-10 cm-1 in either direction), and show variable changes in relative band strengths (typically factors of 1-3). There is little systematic increase or decrease in the band strengths (perhaps none). In H2O-rich ices, naphthalene bands are relatively insensitive to concentration and temperature, with the exception that all the bands show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms. Given the small observed band shifts (

We report infrared spectral evidence of deuterated interstellar polycyclic aromatic hydrocarbons (PAHs). Two bands are detected in the infrared emission from the ionization bar in Orion at 4.4 and 4.65 � m. The one at 4.65 � m is present at the 4.4 � level, while the one at 4.4 � m is more tentative, with aequal to 1.9. An emission band at 4.65 � m is also detected in the infrared emission from M17 by Verstraete and coworkers at the 4.4 � level. These wavelengths are highly characteristic of C-D stretching modes of deuterated PAHs and fall in a featureless region oftheinterstellarspectrum.TheIRspectroscopicpropertiesofdeuteratedPAHsaresummarized,andanestimateof the deuterium fractionation between the aromatic and aliphatic carbons associated with the PAHs is given. High deuterium fractionation is implied; this is discussed in terms of interstellar PAH fractionation mechanisms. Subject headings: astrochemistry — infrared: ISM — ISM: abundances — ISM: molecules — line: identification — techniques: spectroscopic

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.

Ices at ∼15 K consisting of the polycyclic aromatic hydrocarbon coronene (C24H12) condensed either with H2O, CO2, or CO in the ratio of 1 : 100 or greater have been subjected to MeV proton bombardment from a Van de Graaff generator. The resulting reaction products have been examined by infrared transmissionreflection-transmission spectroscopy and by microprobe laser-desorption laser-ionization mass spectrometry. Just as in the case of UV photolysis, oxygen atoms are added to coronene, yielding, in the case of H2O ices, the addition of one or more alcohol ( i OH) and ketone (1CuO) side chains to the coronene scaffolding. There are, however, significant differences between the products formed by proton irradiation and the products formed by UV photolysis of coronene containing CO and CO2 ices. The formation of a coronene carboxylic acid ( i COOH) by proton irradiation is facile in solid CO but not in CO2, the reverse of what was previously observed for UV photolysis under otherwise identical conditions. This work presents evidence that cosmicray irradiation of interstellar or cometary ices should have contributed to the formation of aromatics bearing ketone and carboxylic acid functional groups in primitive meteorites and interplanetary dust particles. Subject headings: astrobiology — astrochemistry — comets: general — cosmic rays — ISM: molecules — molecular processes

Ultraviolet photolysis of various coronene-ice mixtures at low temperature and pressure caused the addition of amino (”NH2), methyl (”CH3), methoxy (”OCH3), cyano/isocyano (”CN, ”NC), and acid (”COOH) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C24H12), in addition to previously reported alcohol (”OH) and ketone (>C»O) formation. This work represents the first experimental evidence that ice photochemistry may have contributed to the aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest that a wide range of modified PAHs should be expected in interstellar ices and materials that predated solar system formation. The implications of these results for interstellar and meteoritic chemistry are discussed. Subject headings: astrobiology — astrochemistry — ISM: molecules — meteors, meteoroids — molecular processes — ultraviolet: ISM

Organic compounds observed in the interstellar medium and in solar system bodies are of particular importance for revealing the chemistry that may have led to life’s origin. Among these compounds, amino acids may have played a crucial role since they are basic components of proteins, which are the essential constituents of all organisms. We present laboratory studies testing the stability of amino acids against ultraviolet (UV) photolysis. Two biological and two nonbiological amino acids have been irradiated in frozen Ar, N2, and H2O to simulate conditions in the interstellar gas and on interstellar grains. The experimental results can be interpreted to indicate that amino acids in the gas phase will likely be destroyed during the lifetime of a typical interstellar cloud. In regions with relatively low UV radiation, amino acids might be present as transient gas-phase species. Their survival in interstellar icy grain mantles and the surface layers of comets and planets is strongly limited in the presence of UV irradiation. The rate of destruction is rather insensitive to the amino acid structure and to the ice matrix. We consider the implications of these results for the survival and transfer of amino acids in space environments, and thus their possible availability for prebiotic chemistry. Subject headings: infrared: ISM: lines and bands — ISM: abundances — ISM: molecules — methods: laboratory — molecular processes

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-1 (4.62 μm) "XCN" absorption feature seen toward embedded protostars such as W33A, we have performed laboratory studies using deuterium (2H) 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 13C, 15N, and 18O labeling experiments that are consistent with previously reported values.

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, 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 triple bond 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, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar 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 triple bond 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-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N2-, CH4-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple ices dominated by N2, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ~ 0.9 and O/C ~ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.

Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C6H6) or naphthalene (C10H8) mixed in ices containing H2O and NH3. This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology.

Nucleobases, together with deoxyribose/ribose and phosphoric acid, are the building blocks of DNA and RNA for all known life. The presence of nucleobase-like compounds in carbonaceous chondrites delivered to the Earth raises the question of an extraterrestrial origin for the molecules that triggered life on our planet. Whether these molecules are formed in interstellar/protostellar environments, in small parent bodies in the solar system, or both, is currently unclear. Recent experiments show that the UV irradiation of pyrimidine (C4H4N2) in H2O-rich ice mixtures that contain NH3, CH3OH, or CH4 leads to the formation of the pyrimidine-based nucleobases uracil, cytosine, and thymine. In this work, we discuss the low-temperature UV irradiation of pyrimidine in realistic astrophysical ice mixtures containing H2O, CH3OH, and NH3, with or without CH4, to search for the production of nucleobases and other prebiotic compounds. These experiments show the presence of uracil, urea, glycerol, hexamethylenetetramine, small amino acids, and small carboxylic acids in all samples. Cytosine was only found in one sample produced from ices irradiated with a higher UV dose, while thymine was not found in any sample, even after irradiation with a higher UV dose. Results are discussed to evaluate the role of the photochemistry of pyrimidine in the inventory of organic molecules detected in meteorites and their astrophysical/astrobiological implications.

Radiation processing of the surface ices of outer solar system bodies may result in the production of new chemical species even at low temperatures. Many of the smaller, more volatile molecules that are likely produced by the photolysis of these ices have been well characterized by laboratory experiments. However, the more complex refractory material formed in these experiments remains largely uncharacterized. In this work, we present a series of laboratory experiments in which low-temperature (15–20 K) N2:CH4:CO ices in relative proportions 100:1:1 are subjected to UV irradiation, and the resulting materials are studied with a variety of analytical techniques including infrared spectroscopy, X-ray absorption near-edge structure spectroscopy, gas chromatography coupled with mass spectrometry, and high-resolution mass spectroscopy. Despite the simplicity of the reactants, these experiments result in the production of a highly complex mixture of molecules from relatively low-mass volatiles (tens of daltons) to high-mass refractory materials (hundreds of daltons). These products include various carboxylic acids, nitriles, and urea, which are also expected to be present on the surface of outer solar system bodies, including Pluto and other transneptunian objects. If these compounds occur in sufficient concentrations in the ices of outer solar system bodies, their characteristic bands may be detectable in the near-infrared spectra of these objects.

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

The infrared emission band spectrum associated with many different interstellar objects can be modeled successfully by using combined laboratory spectra of neutral and positively charged polycyclic aromatic hydrocarbons (PAHs). These model spectra, shown here for the first time, alleviate the principal spectroscopic criticisms previously leveled at the PAH hypothesis and demonstrate that mixtures of free molecular PAHs can indeed account for the overall appearance of the widespread interstellar infrared emission spectrum. Furthermore, these models give us insight into the structures, stabilities, abundances, and ionization balance of the interstellar PAH population. These, in turn, reflect conditions in the emission zones and shed light on the microscopic processes involved in the carbon nucleation, growth, and evolution in circumstellar shells and the interstellar medium.

We present infrared spectra of four embedded protostars in the 750-1230 cm-1 (13.3-8.1 microns) range. For NGC 7538 IRS 9, a new band is reported at 1110 cm-1 (9.01 microns, and several others may be present near 785, 820, 900, 1030, and 1075 cm-1 (12.7, 12.2, 11.1, 9.71, and 9.30 microns). The band 1110 cm-1 is attributed to frozen NH3. Its position and width imply that the NH3 is frozen in a polar, H2O-rich interstellar ice component. The NH3/H2O ice ratio inferred for NGC 7538 IRS 9 is 0.1, making NH3 as important a component as CH3OH and CO2 in the polar ices along this line of sight. At these concentrations, hydrogen bonding between the NH3 and H2O can account for much of the enigmatic low-frequency wing on the 3240 cm-1 (3.09 microns) H2O interstellar ice band. The strength of the implied NH3 deformation fundamental at 1624 cm-1 (6.158 microns) can also account for the absorption at this position reported by ISO.

The infrared spectra of CO frozen in nonpolar ices containing N2, CO2, O2, and H2O and the UV photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140 cm-1 (4.673 microns) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing nonpolar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a 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 N2 and O2 absorptions at 2328 cm-1 (4.296 microns) and 1549 cm-1 (6.456 microns), respectively, are also shown. The best matches between the narrow interstellar band and the feature in the laboratory spectra of nonpolar ices are for samples which contain comparable amounts of N2, O2, CO2, and CO. Co-adding the CO band from an N2:O2:CO2:CO = 1:5:1/2:1 ice with that of an H2O:CO = 20:1 ice provides an excellent fit across the entire interstellar CO feature. The four-component, nonpolar ice accounts for the narrow 2140 cm-1 portion of the feature which is associated with quiescent regions of dense molecular clouds. Using this mixture, and applying the most recent cosmic abundance values, we derive that between 15% and 70% of the available interstellar N is in the form of frozen N2 along several lines of sight toward background stars. This is reduced to a range of 1%-30% for embedded objects with lines of sight more dominated by warmer grains. The cosmic abundance of O tied up in frozen O2 lies in the 10%-45% range toward background sources, and it is between 1% and 20% toward embedded objects. The amount of oxygen tied up in CO and CO2 frozen in nonpolar ices can be as much as 2%-10% toward background sources and on the order of 0.2%-5% for embedded objects. Similarly 3%-13% of the carbon is tied up in CO and CO2 frozen in nonpolar ices toward field stars, and 0.2%-6% toward embedded objects. These numbers imply that most of the N is in N2, and a significant fraction of the available O is in O2 in the most quiescent regions of dense clouds. Ultraviolet photolysis of these ices produces a variety of photoproducts including CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. XCN is not produced in these experiments, placing important constraints on the origin of the enigmatic interstellar XCN feature. N2O and CO3 have not been previously considered as interstellar ice components.

The infrared absorption feature near 2950 cm-1 (3.4 micrometers), 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 m-3 and about 2 to 5 -CH2- groups m-3. These densities are consistent with the strengths of the 2955 and 2925 cm-1 (3.38 and 3.42 micrometers) subfeatures (due to -CH3 and -CH2- groups, respectively) within the overall 2950 cm-1 (3.4 micrometers) band being described by the relations A upsilon/tau(2955 cm-1) = 270 +/- 40 and A upsilon/tau(2925 cm-1) = 250 +/- 40 in the local diffuse ISM.

We report the detection of a broad absorption band at 2165 cm-1 (4.619 microns) in the spectrum of L1551 IRS 5. New laboratory results over the 2200-2100 cm-1 wavenumber interval (4.55-4.76 microns), 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 (both in nonpolar and polar matrices) through absorption bands at 2140 cm-1 (4.67 microns) and 2135 cm-1 (4.68 microns). The relative abundance of solid-state CO to frozen H2O is approximately 0.13 while the abundance of XCN seems comparable to that of frozen CO.

Both laboratory measurements and theory indicate that CO2 should be a common component in interstellar ices. We show that the exact band position, width, and profile of the solid-state 12CO2 infrared bands near 3705, 3600, 2340, and 660 cm-1 (2.70, 2.78, 4.27, and 15.2 micrometers) and the 13CO2 band near 2280 cm-1 (4.39 micrometers) are dependent on the matrix in which the CO2 is frozen. Measurements of these bands in astronomical spectra can be used to determine column densities of solid-state CO2 and provide important information on the physical conditions present in the ice grains of which the CO2 is a part. Depending on the composition of the ice, the CO2 asymmetric stretching band was observed to vary from 2328.7 to 2346.0 cm-1 and have full widths at half-maxima (FWHMs) ranging from 4.7 to 29.9 cm-1. The other CO2 bands showed similar variations. Both position and width are also concentration dependent. Absorption coefficients were determined for the five CO2 bands. These were found to be temperature independent for CO2 in CO and CO2 matrices but varied slightly with temperature for CO2 in H2O-rich ices. For all five bands this variation was found to be less than 15% from 10 to 150 K, the temperature at which H2O ice sublimes. A number of parameters associated with the physical behavior of CO2 in CO2- and H2O-rich ices were also determined. The CO2-CO2 surface binding energy in pure CO2 ices is found to be (delta Hs/k) = 2690 +/- 50 K. CO2-H2O and CO-H2O surface binding energies were determined to be (delta Hs/k) = 2860 +/- 200 K and 1740 +/- 100 K, respectively. Under our experimental conditions, CO2 condenses in measurable quantities into H2O-rich ices at temperatures up to 100 K, only slightly higher than the temperature at which pure CO2 condenses. Once frozen into an H2O-rich ice, the subsequent loss of CO2 upon warming is highly dependent on concentration. For ices with H2O/CO220, the CO is physically trapped within the H2O lattice, and little CO2 is lost until the sublimation temperature of the H2O matrix is reached. In contrast, in ices having H2O/CO25, the CO2 remains only to temperatures of about 90 K. Above this point the CO2 readily diffuses out of the H2O matrix. These results suggest that two different forms of H2O lattice are produced. The implications of these data for cometary models and our understanding of cometary formation are considered.

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.

We present new 3600 - 2700/cm (2.8 - 3.7 micrometer) spectra of objects whose extinction is dominated by dust in the diffuse interstellar medium. The observations presented here augment an ongoing study of the organic component of the diffuse interstellar medium. These spectra contain a broad feature centered near 3300/cm (3.0 micrometers) and/or a feature with a more complex profile near 2950/cm (3.4 micrometers), the latter of which is attributed to saturated aliphatic hydrocarbons in interstellar grains and is the primary interest of this paper. As in our earlier work, the similarity of the absorption bands near 2950/cm (3.4 micrometers) along different lines of sight and the correlation of these features with interstellar extinction reveal that the carrier of this band lies in the dust in the diffuse interstellar medium (DISM). At least 2.5% of the cosmic carbon in the local interstellar medium and 4% toward the Galactic center is tied up in the carrier of the 2950/cm (3.4 micrometer) band. The spectral structure of the diffuse dust hydrocarbon C-H stretch absorption features is reasonably similar to UV photolyzed laboratory ice residues and is quite similar to the carbonaceous component of the Murchison meteorite. The similarity between the DISM and the meteoritic spectrum suggests that some of the interstellar material originally incorporated into the solar nebula may have survived relatively untouched in primitive solar system bodies. Comparisons of the DISM spectrum to hydrogenated amorphous carbon and quenched carbonaceous composite are also presented. The A(sub V)/tau ratio for the 2950/cm (3.4 micrometer) feature is lower toward the Galactic center than toward sources in the local solar neighborhood (approximately 150 for the Galactic center sources vs. approximately 250 for the local ISM sources). A similar trend has been observed previously for silicates in the diffuse medium by Roche & Aitken, suggesting that (1) the silicate and carbonaceous materials in the DISM may be physically correlated and (2) there is either dust compositional variation in the galaxy or galactic variation in the grain population density distribution. We also note a possible absorption feature near 3050/cm (3.28 micrometers), a wavelength position that is characteristic of polycyclic aromatic hydrocarbons (PAHs).

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.

Spectral images in the 3.3 and 11.3 micron IR emission band around the star SVS 3 in NGC 1333 indicate that the two bands have their origin in different locations, rendering them useless in estimates of the sizes of the molecules emitting the bands. This is in keeping with the emission bands' generation by a mixture of variously sized polycyclic aromatic hydrocarbons (PAHs) whose smallest species have been dehydrogenated in the vicinity of SVS 3. Hot bands and overtone/combination bands may account for the 3.4-micron band, rather than molecular side-groups of the PAHs.

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 H20-rich ices can be detected by an infrared absorption band at 4137 cm-1 (2.417 micrometers). The surface binding energy of H2 to H2O ice was measured to the delta Hs/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.

High spectral resolution (nu/delta nu = 900) studies in the 3100-2600 cm-1 (3.2-3.9 microns) range are presented of the protostars NGC 7538 IRS 9, W33A, W3 IRS 5, and S140 IRS 1. This is the spectral region in which the fundamental C-H stretching vibrations of aliphatic hydrocarbons fall. Well-resolved absorption bands at about 2825 cm-1 (3.54 microns) and 2880 cm-1 (3.47 microns) were found superposed on the low-frequency wing of the strong O-H stretch feature. The 2880 cm-1 (3.47 microns) band, a new interstellar feature, is moderately strong in the spectra of all four objects studied. The 2825 cm-1 (3.54 microns) band, previously detected toward W33A, is also in the spectrum of NGC 7538 IRS 9. The relative strength of these two bands varies, showing that they are associated with two different carriers. On the basis of comparisons with laboratory spectra, the 2825 cm-1 (3.54 microns) band is assigned to methanol (CH3OH), in agreement with the earlier work of Grim et al. (1991). This assignment is further supported by a pair of weak absorptions centered at 2600 and 2540 cm-1 (3.85 and 3.94 microns) in the spectrum of W33A recently reported by Geballe (1991). These features compare very well with laboratory spectra of CH3OH/H2O ice mixtures. The CH3OH/H2O ratio derived from the 2825 cm-1 methanol band and the 3250 cm-1 (3.08 microns) H2O feature are 0.13 and 0.40 for NGC 7538 IRS 9 and W33A, respectively. These values are smaller than the ratios of 0.61 and 0.54 derived using the 1460 cm-1 (6.85 microns) band assigned to CH3OH and the 1665 cm-1 (6.00 microns) H2O band. These apparent discrepancies may be due to a combination of scattering effects within the molecular cloud, uncertainties associated with the baselines for the 2825 cm-1 feature, and the presence of other interstellar grain materials that absorb at 1460 cm-1 (6.85 microns). Nonetheless, after H2O, CH3OH is the most abundant known interstellar ice constituent. The new band at about 2880 cm-1 (3.47 microns) falls near the position for C-H stretching vibrations in tertiary carbon atoms. The strength of this feature, in combination with the lack of strong features associated with primary (-CH3) and secondary (-CH2-) carbon atoms, suggests that the carrier of the new feature has a diamond-like structure. We therefore tentatively attribute this new feature to interstellar "diamonds." The detection of this band in the spectra of all four dense molecular clouds suggests that the carrier is ubiquitous in dense clouds. Band-strength analysis indicates that a minimum of a few percent of the available cosmic carbon is tied up in this material.

A search has been made for the strong C-O stretching absorption of solid methanol near 9.8 microns toward the heavily obscured protostars AFGL 961, AFGL 2591, the BN object and Mon R2 IRS 3. There is no clear evidence for this feature in the spectra, resulting in very conservative upper limits to the methanol abundance of 6 percent to 17 percent relative to solid H2O toward these objects. This is well below previous estimates of 50-80 percent obtained toward W33 A, NGC 7538 IRS 9, AFGL 2136, and W3 IRS 5, which were based on the assignment of the interstellar 6.85 microns absorption feature to the methanol C-H bending mode. This study shows that such high methanol abundances are not a characteristic of all interstellar ices.

We have discovered a new IR emission feature at 1905 cm-1 (5.25 microns) in the spectrum of BD +30 degrees 3639. This feature joins the family of well-known IR emission features at 3040, 2940, 1750, 1610, "1310," 1160, and 890 cm-1 (3.3, 3.4, 5.7, 6.2, "7.7," 8.6, and 11.2 microns). The origin of this new feature is discussed and it is assigned to an overtone or combination band involving C-H bending modes of polycyclic aromatic hydrocarbons (PAHs). Laboratory work suggests that spectral studies of the 2000-1650 cm-1 (5.0-6.1 microns) region may be very useful in elucidating the molecular structure of interstellar PAHs. The new feature, in conjunction with other recently discovered spectral structure, suggests that the narrow IR emission features originate in PAH molecules rather than large carbon grains. Larger species are likely to be the source of the broad underlying "plateaus" seen in many of the spectra.

Mesures de la transmission IR de 2,5 a 25 μm de 26 particules de poussieres individuelles de 10 a 40 μm de diametre

A brief discussion of the infrared observations from 4 to 20 micrometers of seven comets is presented. The observed infrared emission from comets depends primarily on their heliocentric distance. A model based on grain populations composed of a mixture of silicate and amorphous carbon particles in the mass ratio of about 40 to 1, with a power-law size distribution similar to that inferred for comet Halley, is applied to the observations. The model provides a good match to the observed heliocentric variation of both the 10 micrometers feature and the overall thermal emission from comets West and Halley. Matches to the observations of comet IRAS-Araki-Alcock and the antitail of comet Kohoutek require slightly larger grains. While the model does not match the exact profile and position of the 3.4 micrometers feature discovered in comet Halley, it does produce a qualitative fit to the observed variation of the feature's strength as a function of heliocentric distance. The calculations predict that the continuum under the 3.4 micrometers feature is due primarily to thermal emission from the comet dust when the comet is close to the Sun and to scattered solar radiation at large heliocentric distances, as is observed. A brief discussion of the determination of cometary grain temperatures from the observed infrared emission is presented. It is found that the observed shape of the emission curve from about 4 to 8 micrometers provides the best spectral region for estimating the cometary grain temperature distribution.

If the "11.3 microns" emission feature seen in the spectra of many planetary nebulae, H II regions, and reflection nebulae is due to polycyclic aromatic hydrocarbons (PAHs), then additional features should be present between 11.3 and 13.0 microns (885 and 770 cm-1). Moderate-resolution spectra of NGC 7027, HD 44179, IRAS 21282+5050, and BD + 30 degrees 3639 are presented which show that the "11.3 microns" feature actually peaks at 11.22 microns (891 cm-1). The spectra also show evidence of new emission features near 11.9 and 12.7 microns (840 and 787 cm-1). These are consistent with an origin from PAHs and can be used to constrain the molecular structure of the family of PAHs responsible for the infrared features. The observed asymmetry of the "11.3 microns" band is consistent with the slight anharmonicity expected in the C--H out-of-plane bending mode in PAHs. Laboratory experiments show that the intensity of this mode relative to the higher frequency modes depends on the extent of molecular "clustering." The observed strengths of the "11.3 microns" interstellar bands relative to the higher frequency bands are most consistent with the features originating from free molecular PAHs. The intensity and profile of the underlying broad structure, however, may well arise from PAH clusters and amorphous carbon particles. Analysis of the 11-13 microns (910-770 cm-1) emission suggests that the molecular structures of the most intensity emitting free PAHs vary somewhat between the high-excitation environment in NGC 7027 and the low-excitation but high-flux environment close to HD 44179. Finally, a previously undetected series of regularly spaced features between 10 and 11 microns (1000 and 910 cm-1) in the spectrum of HD 44179 suggests that a simple polyatomic hydride is present in the gas phase in this object.

Analysis of laboratory spectra of numerous astrophysical ice analogs demonstrates that the exact band position, width, and profile of the solid state CO fundamental near 2137 cm-1 (4.679 microns) can provide important information on the physical conditions present during the ice accretion phase as well as during any subsequent thermal processes and radiation exposure. In the ices studied, the CO peak position varies from 2134 to 2144 cm-1 (4.686 to 4.664 microns) and the band width from 2.1 to over 20 cm-1 depending on the composition of the ice. In an ice matrix dominated by H2O, the CO peak falls at 2136.7 cm-1, has a full width at half-maximum of about 9 cm-1, and shows a prominent sideband at 2152 cm-1. This sideband and minor structure superposed on the main band arise from CO trapped in different matrix sites. These features provide information concerning the thermal and radiation history of the ice. The solid CO band in interstellar spectra often has contributions from broad (12 cm-1) and narrow (5 cm-1) components. We identify the broad component with CO intimately mixed in matrices dominated by polar molecules, of which H2O is likely to be the major component. Examination of the interstellar and laboratory band profiles shows that either the abundance of nonpoplar impurities in these ices must be less than 10% or the ices have been thermally annealed or processed by ultraviolet radiation. The narrow component is likely to originate from grain mantles dominated by nonpolar molecules such as CO2. These components reflect differences in the physical and chemical conditions in regions of the cloud along the line of sight. Laboratory determination of the absorption strength of the CO fundamental in H2O-rich ices showed that the value used in the past was approximately 60% too low and that most previously determined solid-state CO column densities have been systematically overestimated. The rich spectral behavior of the CO band observed in the laboratory studies clearly indicates that future high-quality astronomical spectra in the 2200-2100 cm-1 range can produce a wealth of new information and provide deeper insights into the nature of astrophysical ices.