Interstellar organics and possible connections with the carbonaceous components of meteorites and IDPs

Studying the chemical and isotopic composition of interstellar ice and dust provides insight into the composition and chemical history of the solid bodies in the solar nebula and the nature of the materials subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to probe the composition of these microscopic interstellar particles. High quality IR spectra of many different astronomical sources (some associated with dark molecular clouds, and others in the diffuse interstellar medium) are now available. Comparisons of these spectra with laboratory spectra and complex organic components of these materials are discussed

The origin, composition and history of cometary ices from spectroscopic studies

The spectroscopic analysis of pristine cometary material provides a very important probe of the chemical identity of the material as well as of the physical and chemical conditions which prevailed during the comet's history. Concerning classical spectroscopy, the spectral regions which will most likely prove most useful are the infrared, the visible and ultraviolet. Newer spectroscopic techniques which have the potential to provide equally important information include nuclear magnetic resonance (NMR) and electron spin resonance (ESR). Each technique is summarized with emphasis placed on the kind of information which can be obtained

Interstellar grain chemistry and organic molecules

The detection of prominant infrared absorption bands at 3250, 2170, 2138, 1670 and 1470 cm(-1) (3.08, 4.61, 4.677, 5.99 and 6.80 micron m) associated with molecular clouds show that mixed molecular (icy) grain mantles are an important component of the interstellar dust in the dense interstellar medium. These ices, which contain many organic molecules, may also be the production site of the more complex organic grain mantles detected in the diffuse interstellar medium. Theoretical calculations employing gas phase as well as grain surface reactions predict that the ices should be dominated only by the simple molecules H2O, H2CO, N2, CO, O2, NH3, CH4, possibly CH3OH, and their deuterated counterparts. However, spectroscopic observations in the 2500 to 1250 cm(-1)(4 to 8 micron m) range show substantial variation from source reactions alone. By comparing these astronomical spectra with the spectra of laboratory-produced analogs of interstellar ices, one can determine the composition and abundance of the materials frozen on the grains in dense clouds. Experiments are described in which the chemical evolution of an interstellar ice analog is determined during irradiation and subsequent warm-up. Particular attention is paid to the types of moderately complex organic materials produced during these experiments which are likely to be present in interstellar grains and cometary ices

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3. The Polyacenes Anthracene, Tetracene, and Pentacene

Gaseous, ionized Polycyclic Aromatic Hydrocarbons (PAH's) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAH's. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400 / cm (between about 1340 and 1500 / cm) and near 1180 /cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family

Clathrate type 2 hydrate formation in vacuo under astrophysical conditions

The properties of clathrate hydrates were used to explain the complex and poorly understood physical processes taking place within cometary nuclei and other icy solar system bodies. Most of all the experiments previously conducted used starting compositions which would yield clathrate types I hydrates. The main criterion for type I vs. type II clathrate hydrate formation is the size of the guest molecule. The stoichiometry of the two structure types is also quite different. In addition, the larger molecules which would form type II clathrate hydrates typically have lower vapor pressures. The result of these considerations is that at temperatures where we identified clathrate formation (120-130 K), it is more likely that type II clathrate hydrates will form. We also formed clathrate II hydrates of methanol by direct vapor deposition in the temperature range 125-135 K

Low-pressure clathrate-hydrate formation in amorphous astrophysical ice analogs

In modeling cometary ice, the properties of clathrate hydrates were used to explain anomalous gas release at large radial distances from the Sun, and the retention of particular gas inventories at elevated temperatures. Clathrates may also have been important early in solar system history. However, there has never been a reasonable mechanism proposed for clathrate formation under the low pressures typical of these environments. For the first time, it was shown that clathrate hydrates can be formed by warming and annealing amorphous mixed molecular ices at low pressures. The complex microstructures which occur as a result of clathrate formation from the solid state may provide an explanation for a variety of unexplained phenomena. The vacuum and imaging systems of an Hitachi H-500H Analytical Electron Microscope was modified to study mixed molecular ices at temperatures between 12 and 373 K. The resulting ices are characterized by low-electron dose Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED). The implications of these results for the mechanical and gas release properties of comets are discussed. Laboratory IR data from similar ices are presented which suggest the possibility of remotely observing and identifying clathrates in astrophysical objects

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations

Gaseous, ionized polycyclic aromatic hydrocarbons (PAHs) are thought to be responsible for a very common family of interstellar infrared emission bands. Here the near- and mid-infrared spectra of the cations of the five most thermodynamically favored PAHs up to coronene: phenanthrene, pyrene, benzo(e)pyrene, benzo-(ghi)perylene, and coronene, are presented to test this hypothesis. For those molecules that have been studied previously (pyrene, pyrene-d(sub 10), and coronene), band positions and relative intensities are in agreement. In all of these cases we report additional features. Absolute integrated absorbance values are given for the phenanthrene, perdeuteriophenanthrene, pyrene, benzo(ghi]perylene, and coronene cations. With the exception of coronene, the cation bands corresponding to the CC modes are typically 2-5 times more intense than those of the CH out-of-plane bending vibrations. For the cations, the CC stretching and CH in-plane bending modes give rise to bands that are an order of magnitude stronger than those of the neutral species, and the CH out-of-plane bends produce bands that are 5-20 times weaker than those of the neutral species. This behavior is similar to that found in most other PAH cations studied to date. The astronomical implications of these PAH cation spectra are also discussed

Properties of Polycyclic Aromatic Hydrocarbons in the Northwest Photon Dominated Region of NGC 7023. I. PAH Size, Charge, Composition, and Structure Distribution

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer Infrared Spectrograph spectral map of the northwest photon dominated region (PDR) in NGC 7023 was analyzed exclusively using PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb). The 5-15 micron spectrum at each pixel is fitted using a non-negative-least-squares fitting approach. The fits are of good quality, allowing decomposition of the PAH emission into four subclasses: size, charge, composition, and hydrogen adjacency (structure). Maps tracing PAH subclass distributions across the region paint a coherent astrophysical picture. Once past some 20 seconds of arc from HD 200775, the emission is dominated by the more stable, large, symmetric, compact PAH cations with smaller, neutral PAHs taking over along the lines-of-sight toward the more distant molecular cloud. The boundary between the PDR and the denser cloud material shows up as a distinct discontinuity in the breakdown maps. Noteworthy is the requirement for PANH cations to fit the bulk of the 6.2 and 11.0 micron features and the indication of PAH photo-dehydrogenation and fragmentation close to HD 200775. Decomposition of the spectral maps into "principal" subclass template spectra provides additional insight into the behavior of each subclass. However, the general applicability of this computationally more efficient approach is presently undetermined. This is the first time the spectra of individual PAHs are exclusively used to fit the 5-15 micron region and analyze the spatial behavior of the aromatic infrared bands, providing fundamental, new information about astronomical PAH subpopulations including their dependence on, and response to, changes in local conditions

The Role of Polycyclic Aromatic Hydrocarbons in Ultraviolet Extinction. I. Probing small molecular PAHs

We have obtained new STIS/HST spectra to search for structure in the ultraviolet interstellar extinction curve, with particular emphasis on a search for absorption features produced by polycyclic aromatic hydrocarbons (PAHs). The presence of these molecules in the interstellar medium has been postulated to explain the infrared emission features seen in the 3-13 $\mu$m spectra of numerous sources. UV spectra are uniquely capable of identifying specific PAH molecules. We obtained high S/N UV spectra of stars which are significantly more reddened than those observed in previous studies. These data put limits on the role of small (30-50 carbon atoms) PAHs in UV extinction and call for further observations to probe the role of larger PAHs. PAHs are of importance because of their ubiquity and high abundance inferred from the infrared data and also because they may link the molecular and dust phases of the interstellar medium. A presence or absence of ultraviolet absorption bands due to PAHs could be a definitive test of this hypothesis. We should be able to detect a 20 \AA wide feature down to a 3$\sigma$ limit of $\sim$0.02 A$_V$. No such absorption features are seen other than the well-known 2175 \AA bump.Comment: 16 pages, 3 figure, ApJ in pres