Interstellar hydrogen bonding

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.     

Observational astrochemistry

Astronomers have identified some 70 molecular species in dense interstellar clouds and the envelopes expelled by evolved stars. Some 75% of these are organic, including molecules with up to 13 atoms and with weights up to 147 daltons. Elements found in interstellar compounds include H, C, N, O, S, Si, and probably Cℓ. A recent addition to the list of interstellar molecules is the first hydrocarbon ring, cyclopropenylidene (C₃H₂). Current research in astrochemistry is concentrating on the determination of accurate chemical abundances as a function of environment. Both basic similarities and intriguing differences among clouds are found, which may provide clues to processes associated with cloud evolution and star formation.     

Fullerenes in space.

The discovery and synthesis of fullerenes led to the hypothesis that they may be present and stable in interstellar space. Fullerenes have been reported in an impact crater on the LDEF spacecraft. Investigations of fullerenes in carbonaceous meteorites have yielded only small upper limits. Fullerene compounds and their ions could be interesting carrier molecules for some of the "diffuse interstellar bands" (DIBs), a long standing mystery in astronomy. We have detected two new diffuse bands that are consistent with laboratory measurements of the C60+, as first evidence for the largest molecule ever detected in space. Criteria for this identification are discussed. The inferred abundance (up to 0.9 % of cosmic carbon locked in C60+) suggests that fullerenes may play an important role in interstellar chemistry. We present new observations on DIB substructures consistent with fullerene compounds, and the search for neutral C60 in the diffuse medium.     

Chemical evolution of primitive solar system bodies.

In this paper we summarize some of the most salient observations made recently on the organic molecules and other compounds of the biogenic elements present in the interstellar medium and in the primitive bodies of the solar system. They include the discovery of the first phosphorus molecular species in dense interstellar clouds, the presence of complex organic ions in the dust and gas phase of Halley's coma, the finding of unusual, probably presolar, deuterium-hydrogen ratios in the amino acids of carbonaceous chondrites, and new developments on the chemical evolution of Titan, the primitive Earth, and early Mars. Some of the outstanding problems concerning the synthesis of organic molecules on different cosmic bodies are also discussed from an exobiological perspective.     

Chemical evolution and the origin of life.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.     

Production and evolution of carbonaceous material by ion irradiation in space.

We review recent experimental studies concerning the evolution, driven by ion irradiation, of carbonaceous material from frozen gas to a refractory molecular solid. Under further irradiation the latter changes to a polymer-like material and ultimately to amorphous carbon. Most of the results have been obtained by "in situ" and remote IR and Raman spectroscopy. The results have been applied to demonstrate that molecular solids may be easily formed by irradiation of frozen mantles in dense interstellar clouds. Polymer-like material and amorphous carbons may result by further irradiation of organic mantles on grains in the diffuse interstellar medium. Those grains, during the aggregation to form extended bodies like comets (T-Tau phase of the Sun), are further modified. These latter are also irradiated, after the comet formation, during their long stay in the Oort cloud. In particular it has been suggested that comet may develop an ion-produced cometary organic crust that laboratory evidences show to be stable against temperature increases experienced during passages near the Sun. The comparison between the Raman spectra of some IDP (Interplanetary Dust Particles) and the Raman spectra of some ion-produced amorphous carbons, is also discussed.     

Circumstellar chemistry from microwave and mm-wave spectroscopy.

Stars in their late stages of evolution often shed matter in the form of a cool wind which is molecular in composition. These winds are a major source of replenishment of the interstellar gas and dust, so they furnish a large part of the raw materials for new generations of stars and planets. The chemistry of the circumstellar envelope depends strongly on the photospheric abundances of the elements, especially C and O. If C/O > 1, a rich organic chemistry is observable in the microwave and mm-wavelength emission lines of the reactions products. This paper reviews the observational evidence for the presence of organic molecules and their formation pathways in circumstellar envelopes, with special emphasis on rotational spectra at microwave and millimeter wavelengths.     

The composition and distribution of anomalous cosmic rays

The composition of anomalous cosmic rays (ACR), is thought to reflect that of the neutral atoms in the very local interstellar medium, such as helium, nitrogen and neon. Recent observations in the outer heliosphere have provided the first unambiguous evidence for ACR argon, carbon and hydrogen, as well, and a method has been developed to relate the ACR abundances to those of the interstellar medium. The observations also indicate persistent negative latitudinal gradients, opposite to that observed by Pioneer 11 during the previous minimum in solar activity. These and other results are consistent with the presence of gradient and curvature drift during solar minimum periods when the tilt of the interplanetary neutral sheet is small.     

A laboratory model for interstellar chemical evolution.

The chemistry in a supersonic plasma source flow was studied as a laboratory model for interstellar chemical evolution. It is important to match the similarity parameters for cosmic and laboratory conditions, which connect the temporal and spatial scales of the two cases. The apparatus simulated the conditions in a molecular cloud with respect to molecular-ionic reaction fraction, temperature, and non-equilibrium kinetics. The plasma flow was found to be cold enough, by the radical expansion, to produce polyatomic molecules. From the simple atomic plasma as reactant, cyanopolyyne and unsaturated hydrocarbons were synthesized in the present experiment. These molecules are also inherent in molecular clouds. The reaction mechanism is discussed.     

On the possible detection of solid O2 and O3 interstellar grains with ISO

In various models of interstellar grain chemistry, solid O₂ is formed by accretion as well as by surface reactions on grains. In dense molecular cloud models, at a later stage of the evolution, the O₂ molecule may become a substantial grain mantle constituent. Since IR dipole vibrational transitions for the homonuclear diatomic molecule O₂ are forbidden, the abundance of this potentially important grain mantle component can not be determined. However, embedded in a dirty ice matrix, the fundamental vibration of O₂ at 1550 cm⁻¹ becomes observable at 10 K, due to interactions with surrounding molecules, which break the symmetry of molecular oxygen. This process might be applicable for the dust mantle environment of interstellar grains. We have studied the role of solid O₂ and O₃ in astrophysically relevant ice mixtures and discuss the possible detection of solid O₂ and its major photolysis product O₃ in interstellar grains, in dense molecular clouds. Both molecules represent a specific target to be observed by the ISO satellite in the near future.     

Laboratory simulation of the photoprocessing and warm-up of cometary and pre-cometary ices: production and analysis of complex organic molecules.

The possibility that the organic molecules that have been found near comets could have formed by UV photolysis of interstellar ices was investigated by simulating this process in the laboratory. It is found that oxygen rich organics containing C-OH, C-H and C=O groups are readily produced in this way. These results indicate that part of the organic material in comets may have formed by UV irradiation of ices, either in the pre-solar nebula or in the interstellar phase.     

Photospheric composition and structure in white dwarfs

One of the central mysteries of white dwarf studies has been the nature and abundance of trace elements in the atmospheres of these stars. It had been thought that the dominant trace element in otherwise pure hydrogen DA white dwarf atmospheres was helium. However, some spectroscopic and theoretical evidence suggested that, at least in some stars, heavier elements may be important. Prior to the launch of ROSAT the questions regarding the atmospheric composition of DA white dwarfs in general remained unresolved. The ROSAT mission has provided EUV and X-ray data for a large sample of DA white dwarfs with which we can study their photospheric composition and structure through the effect of trace opacity sources on the emergent fluxes. Contrary to expectations little (if any) helium is found and the main sources of opacity appear to be trace heavy elements. Support for these conclusions is found in recent EUV and far-UV spectra of several stars. However, photometric data do not allow us to determine the abundance of the individual elements and observations with the EUVE spectrometers will be essential for detailed composition measurements.     

Comets in other planetary systems?

Comets in our solar system appear to have provided a bridge between the cold, volatile-rich outer solar system, and the warm, but volatile-poor inner solar system. Excluding tidal and possible extinct radionuclide heating sources, only in the inner solar system are temperatures high enough for liquid water, and therefore life as we know it, to exist for times comparable to the age of the solar system. Comets may have been crucial for providing biogenic volatiles and perhaps organic molecules to this warm environment. It is therefore interesting from an exobiological point of view to ask if comets exist in other planetary systems. Most attempts to detect comets around other stars or in interstellar space have failed. However, there is growing spectroscopic evidence for comet-like bodies orbiting the star Beta Pictoris.     

Catalytic activity of interstellar grains: Formation of molecular hydrogen on amorphous silicates

Silicates constitute an important class of interstellar grain material and are the site of catalytic activities, most notably the formation of molecular hydrogen. Here we report an analysis of experiments conducted in the laboratory to measure the efficiency of formation of molecular hydrogen on amorphous silicates, a realistic analogue of interstellar dust grains. From the measurements, we also obtain the energetics of key processes in the reaction and information on the mechanism of reaction. Comparison with earlier measurements of molecular hydrogen formation on a sample of polycrystalline olivine shows that amorphous materials are more efficient catalysts.     

Characteristics and formation of amino acids and hydroxy acids of the Murchison meteorite.

Eight characteristics of the unique suite of amino acids and hydroxy acids found in the Murchison meteorite can be recognized on the basis of detailed molecular and isotopic analyses. The marked structural correspondence between the alpha-amino acids and alpha-hydroxy acids and the high deuterium/hydrogen ratio argue persuasively for their formation by aqueous phase Strecker reactions in the meteorite parent body from presolar, i.e., interstellar, aldehydes, ketones, ammonia, and hydrogen cyanide. The characteristics of the meteoritic suite of amino acids and hydroxy acids are briefly enumerated and discussed with regard to their consonance with this interstellar-parent body formation hypothesis. The hypothesis has interesting implications for the organic composition of both the primitive parent body and the presolar nebula.     

The seeding of life by comets.

The evidence that living organisms were already extant on the earth almost 4 Gyr ago and that early bombardment by comets and asteroids created a hostile environment up to about this time has revived the question of how it was possible for prebiotic chemical evolution to have provided the necessary ingredients for life to have developed in the short intervening time. The actual bracketed available temporal space is no more than 0.5 Gyr and probably much less. Was this sufficient time for an earth-based source of the first simple organic precursor molecules to have led to the level of the prokaryotic cell? If not, then the difficulty would be resolved if the ancient earth was impregnated by organic molecular seed from outer space. Curiously, it seems that the most likely source of such seeds was the same a one of the sources of the hostile enviroment, namely the comets which bombarded the earth. With the knowledge of comets gained by the space missions it has become clear that a very large fraction of the chemical composition of comet nuclei consists of quite complex organic molecules. Furthermore it has been demonstrated that comets consist of very fluffy aggregates of interstellar dust whose chemistry derives from photoprocessing of simple ice mixtures in space. Thus, the ultimate source of organics in comets comes from the chemical evolution of interstellar dust. An important and critical justification for assuming that interstellar dust is the ultimate source of prebiotic molecular insertion on the earth is the proof that comets are extremely fluffy aggregates, which have the possibility of breaking up into finely divided fragments when the comet impacts the earth's atmosphere. In the following we will summarize the properties of interstellar dust and the chemical and morphological structure of comets indicated by the most recent interpretations of comet observations. It will be shown that the suitable condition for comets having provided abundant prebiotic molecules as well as the water in which they could have further evolved are consistent with theories of the early earth environment.     

IUE observations of hot stars

Stellar winds are found in hot and luminous stars of all types. We see evidence of these winds in P Cygni profiles of resonance lines in the UV spectral regions, and obtain density information from them, and from optical emission lines and from free-free radiation in the infrared and radio continua from the ionized plasma. Data recently acquired from the IUE satellite are now sufficient to enable us to outline the broad parameters of these winds. It is found that for the hottest stars, those of 0-type, the mass loss rate ? is proportional to L^α. A proportionality between ? and L is predicted by the theory of radiatively driven winds; the value for α is also anticipated by the details of the theory. The dispersion of individual stellar values may be due to observational uncertainty alone, but it may also suggest that other physical parameters affect the stellar winds. The kinetic energy input of the stellar winds to the interstellar medium is considerable and may, in aggregate, be of the same order as the contribution of supernovae.     

Structure and NIR feature of QCC: a laboratory analog of carbon dust.

We have produced thin films of quenched carbonaceous composite (QCC) by hydrocarbon plasma deposition. The effect of thermal annealing on QCC has been investigated to understand how QCC, as a laboratory analog of carbon dust, is transformed in the warm environment around evolved stars. Spectroscopic measurements have indicated that, by heating, the proportion of aromatic sp2 CH bonds increases relative to sp3 CH bonds. Carbon onion-like spherules of approximately 10 nm in diameter are found with electron microscopic images after "graphitization" of thermal annealing.     

Similarity of the infrared spectrum of an Orgueil organic polymer with interstellar organic compounds in the line of sight towards IRS 7.

We present a comparison between the IR spectrum of the galactic center source IRS 7 and the spectrum of a carbonaceous polymer from the Orgueil meteorite. We have obtained an almost perfect match between the two spectra in the region between 3020-2790 cm-1, which suggests that the chemical composition of the interstellar organic matter and that of the meteorite polymer are similar or that the meteoritic polymer could be a well preserved interstellar organic molecule. Assuming that the meteoritic polymer has the same C/H ratio as these interstellar molecules, we find that 45 % of the total abundance of carbon in the line of sight toward IRS 7 is trapped in such an interstellar organic grain material.