Interstellar molecules and the problem of laboratory data

The use of interstellar molecules as probes of physical conditions in interstellar clouds is hampered by the lack of basic laboratory data. The excitation of interstellar molecules is poorly understood because the nature of the interaction of molecules with radiation and with neutral particles is largely undknown. The mechanisms of formation and destruction of interstellar molecules are presently speculative, because little data exists in such areas as gas-phase ion-molecule reactions and exchange reactions, and reactions of various types on surfaces. Specific needs with regard to laboratory data are discussed in these and other areas. Operated by Associated Universities, Inc., under contract with the National Science Foundation.     

The inventory of interstellar materials available for the formation of the solar system

Tremendous progress has been made in the field of interstellar dust in recent years through the use of telescopic observations, theoretical studies, laboratory studies of analogs, and the study of actual interstellar samples found in meteorites. It is increasingly clear that the interstellar medium (ISM) contains an enormous diversity of materials created by a wide range of chemical and physical processes. This understanding is a far cry from the picture of interstellar materials held as recently as two decades ago, a picture which incorporated only a few generic types of grains and few molecules. In this paper, I attempt to review some of our current knowledge of the more abundant materials thought to exist in the ISM. The review concentrates on matter in interstellar dense molecular clouds since it is the materials in these environments from which new stars and planetary systems are formed. However, some discussion is reserved for materials in circumstellar environments and in the diffuse ISM. The paper also focuses largely on solid materials as opposed to gases since solids contain a major fraction of the heavier elements in clouds and because solids are most likely to survive incorporation into new planetary systems in identifiable form. The paper concludes with a discussion of some of the implications resulting from the recent growth of our knowledge about interstellar materials and also considers a number of areas in which future work might be expected to yield important results.     

Influence of uncertainties in the rate constants of chemical reactions on astrochemical modeling results

We analyze the influence of errors in the rate constants of gas-phase chemical reactions on the model abundances of molecules in the interstellar medium using the UMIST 95 chemical database. By randomly varying the rate constants within the limits of the errors given in UMIST 95, we have estimated the scatters in theoretical abundances for dark and diffuse molecular clouds. All of the species were divided into six groups by the scatter in their model equilibrium abundances when varying the rate constants of chemical reactions. The distribution of the species in groups depends on the physical conditions. The scatters in the abundances of simple species lie within 0.5–1 order of magnitude, but increase significantly as the number of atoms in the molecule increases. We suggest a simple method for identifying the reactions whose rate constants have the strongest effect on the abundance of a selected species. This method is based on an analysis of the correlations between the abundance of species and the reaction rate constants and allows the extent to which an improvement in the rate constant of a specific reaction reduces the uncertainty in the abundance of the species concerned to be directly estimated.     

Calculations on the rates, mechanisms, and interstellar importance of the reactions between C and NH2 and between N and CH2

The attempt to understand the temperature dependence of the HNC/HCN abundance ratio in interstellar clouds has been long standing and indecisive. In this paper we report quantum chemical and dynamical studies of two neutral–neutral reactions thought to be important in the formation of HNC and HCN, respectively – C+NH₂→HNC+H, and N+CH₂→HCN+H. We find that although these reactions do lead initially to the products suggested by astronomers, there is so much excess energy available in both reactions that the HCN and HNC products are able to undergo efficient isomerization reactions after production. The isomerization leads to near equal production rates of the two isomers, with HNC slightly favoured if there is sufficient rotational excitation. This result has been incorporated into our latest chemical model network of dense interstellar clouds.     

Protosolar nebula and composition of comets

Comets seem to be composed of matter, which is supposed to have the same molecular composition as protosolar nebula. Although there are no unbiased evidence that cometary nuclei retain the molecular composition inherited from the protosolar cloud, the observed properties of comets indicate that there is at least a resemblance between cometary composition and the material properties of dense interstellar clouds. Therefore the origin of comets could be searched in the cold stages of the protosolar nebula and molecular abundances of grain mantles in this nebula may be similar to those in the cometary dust. It is suggested that comets may contain pristine, virtually unaltered protosolar material and their study might be very relevant way to more information about processes in early stages of the solar nebula. Our knowledge about composition of the cometary nucleus is still relatively scarce, but we can partly deduce it from data obtained either by ground-based spectroscopy or by in situ mass spectrometry from space experiments. Most important were the discovery of fluffy CHON particles composed partly or even completely from compounds containing light elements. No consensus concerning the presence of interstellar pristine matter in comet has been reached from various approaches to determine the relationship between comets and interstellar grains. Most of these studies are based on infrared spectroscopy. Another method is the comparison on the chemical models of the protosolar nebula with the volatile compounds of the cometary nuclei. Both gas-phase and grain-surface chemistry are considered and initial gas-phase atomic abundances are assumed to be protosolar. The cometary matter is certainly not identical with the typical material of dense interstellar cool dense clouds, but it is closer to it than any other type of matter in solar system so far accessible to us. The data from comets combined with models of chemical evolution of matter in environment similar as prevailed the early stage of presolar nebula may at least impose constrains on the condition for comet formation. Here presented study is a preliminary contribution to such studies.     

Dust particles in the atmospheres of terrestrial planets and their roles for prebiotic chemistry: An overview

The available literature on sources, chemical composition, and importance of dust particles for the origins of life is analyzed. The most abundant sources of dust on the early terrestrial planets are sedimentation of interplanetary dust, meteoritic/cometary impacts, and volcanic eruptions. Interplanetary dust can originate directly from interstellar space, from evaporation of cometary bodies, from collisional destruction of asteroidal and meteoritic bodies, and nucleation in sunspots. Many rather complex organic species, including those of prebiotic interest, have been identified in the interstellar medium and cometary dust. Some of them are believed to formvia catalytic processes on the surfaces of dust particles. However, the mechanisms are not known, and even simulating experiments are difficult to perform due to insufficient knowledge of physical conditions in the space media and of chemical composition and properties of the dust. Besides the catalytic roles, cometary dust is believed to be the best delivery vehicle for organic matter of space origin to the atmospheres of terrestrial planets. Abundant sources of catalytically active fine dust can be volcanoes. Various organic and biological compounds have been found in terrestrial volcanic gases and ash, which are assumed to formvia the catalytic Fischer-Tropsch reactions. At present the eruptions on the Earth provide a unique opportunity to observein situ the formation of organic matter, and knowledge of the ash composition and local conditions allows to perform simulating experiments.     

The effect of grain size distribution on H2 formation rate in the interstellar medium

The formation of molecular hydrogen  (H₂)  in the interstellar medium takes place on the surfaces of dust grains. Hydrogen molecules play a role in gas-phase reactions that produce other molecules, some of which serve as coolants during gravitational collapse and star formation. Thus, the evaluation of the production rate of hydrogen molecules and its dependence on the physical conditions in the cloud are of great importance. Interstellar dust grains exhibit a broad size distribution in which the small grains capture most of the surface area. Recent studies have shown that the production efficiency strongly depends on the grain composition and temperature as well as on its size. In this paper, we present a formula that provides the total production rate of  H₂  per unit volume in the cloud, taking into account the grain composition and temperature as well as the grain size distribution. The formula agrees very well with the master equation results. It shows that for a physically relevant range of grain temperatures, the production rate of  H₂  is significantly enhanced due to their broad size distribution.     

Dust-induced chemical differentiation in dense regions

Dust grains respond to the physical and chemical conditions of the interstellar region in which they are embedded. The interaction produces an extinction curve which depends on the local environment and on the past history of the dust grains. In this work we present a theoretical study of the effects of radial variations of dust extinction properties on gas-phase chemistry in spherical core–halo clouds. We use observational constraints on the variation range of the extinction curve, and we analyse if the degree of dust environmental processing could be reflected by chemical signatures in the gas-phase molecular concentrations. The results of this work show that significant variations in the photodestruction rates and in the thermal profile of the cloud might induce chemical patterns otherwise excluded in the standard dense-cloud chemistry. Some discrepancies between observations and theoretical provisions are discussed in the light of the present results.     

Two populations of open star clusters in the Galaxy

Based on our compiled catalogue of fundamental astrophysical parameters for 593 open clusters, we analyze the relations between the chemical composition, spatial positions, Galactic orbital elements, age, and other physical parameters of open star clusters. We show that the population of open clusters is heterogeneous and is divided into two groups differing by their mean parameters, properties, and origin. One group includes the Galactic clusters formed mainly from the interstellar matter of the thin disk with nearly solarmetallicities ([Fe/H] > ?0.2) and having almost circular orbits a short distance away from the Galactic plane, i.e., typical of the field stars of the Galactic thin disk. The second group includes the peculiar clusters formed through the interaction of extragalactic objects (such as high-velocity clouds, globular clusters, or dwarf galaxies) with the interstellar matter of the thin disk, which, as a result, derived abnormally low (for field thin-disk stars) metallicities and/or Galactic orbits typical of objects of the older Galactic subsystems. About 70% of the clusters older than 1Gyr have been found to be peculiar, suggesting a slower disruption of clusters with noncircular high orbits. Analysis of orbital elements has shown that the bulk of the clusters from both groups were formed within a Galactocentric radius of ??10.5 kpc and closer than ??180 pc from the Galactic plane, but owing to their high initial velocities, the peculiar clusters gradually took up the volumes occupied by the objects of the thick disk, the halo, and even the accreted halo of the Galaxy. Analysis of the relative abundances of magnesium (a representative of the ??-elements) in clusters that, according to their kinematical parameters, belong to different Galactic subsystems has shown that all clusters are composed of matter incorporating the interstellar matter of a single protogalactic cloud in different proportions, i.e., reprocessed in genetically related stars of the Galaxy. The [Mg/Fe] ratios for the clusters with thick-disk kinematics are, on average, overestimated, just as for the field stars of the socalled ??metal-rich wing?? of the thick disk. For the clusters with halo kinematics, these ratios exhibit a very large spread, suggesting that they were formed mainly from matter that experienced a history of chemical evolution different from the Galactic one. We point out that a large fraction of the open clusters with thindisk kinematics have also been formed from matter of an extragalactic nature within the last ??30 Myr.     

Assessment of the interstellar processes leading to deuterium enrichment in meteoritic organics

Abstract— The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low‐temperature gas phase ion‐molecule reactions, low‐temperature gas‐grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D‐enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, O, and N in the same compounds.     

Some `Solid Facts' on Interstellar Dust

Despite considerable observational information on infrared absorption and emission spectra of interstellar matter, together with extensive laboratory data on the spectra of possible constituents, there are presently few firm identifications of individual chemical components. Simple chemical compounds including H₂O, CO and CO₂ are detected in dust in dark interstellar clouds, but other molecules such as ethane, acetylene and benzene do not appear to be present with appreciable abundance. Nevertheless, IR spectra show that hydrocarbons are aubiquitous component of interstellar matter. The nature of these materials and their relation to specific molecular components is discussed in this paper. This revised version was published online in July 2006 with corrections to the Cover Date.     

New models of interstellar gas–grain chemistry – II. Surface photochemistry in quiescent cores

The photodissociation of surface species, caused by photons from the cosmic-ray-induced and background interstellar radiation fields, is incorporated into our combined gas-phase and grain-surface chemical models of quiescent dense interstellar cores. For the cores studied here, only cosmic-ray-induced photons are important. We find that photodissociation alters gas-phase and surface abundances mainly at large cloud ages (≳ 10^6–7 yr). The abundances of those surface species, such as H₂O, that are readily reproduced on the surface following photodissociation are not strongly affected at any time. The abundances of surface species that are, on the other hand, reformed slowly via surface reactions possessing activation energy (e.g. CH₃OH) are reduced, while the abundances of associated surface photoproducts (e.g. CO) increase. In the gas phase, inclusion of surface photodissociation tends to increase molecular abundances at late times, slightly improving the agreement with observation for TMC-1.     

On water ice formation in interstellar clouds

A model is proposed for the formation of water ice mantles on grains in interstellar clouds. This occurs by direct accretion of monomers from the gas, be they formed by gas or surface reactions. The formation of the first monolayer requires a minimum extinction of interstellar radiation, sufficient to lower the grain temperature to the point where thermal evaporation of monomers is just offset by monomer accretion from the gas. This threshold is mainly determined by the adsorption energy of water molecules on the grain material; for hydrocarbon material, chemical simulation places this energy between 0.5 and 2 kcal mol⁻¹, which sets the (true) visible extinction threshold at a few magnitudes. However, realistic distributions of matter in a cloud will usually add to this an unrelated amount of cloud core extinction, which can explain the large dispersion of observed (apparent) thresholds. Once the threshold is crossed, all available water molecules in the gas are quickly adsorbed, because the grain cools down and the adsorption energy on ice is higher than on bare grain. The relative thickness of the mantle, and, hence, the slope of  τ₃( A _v)  depend only on the available water vapour, which is a small fraction of the oxygen abundance. Chemical simulation was also used to determine the adsorption sites and energies of O and OH on hydrocarbons and study the dynamics of formation of water molecules by surface reactions with gaseous H atoms, as well as their chances to stick in situ.     

Masers in star-forming regions

Maser action in the interstellar medium produces the brightest and most spectacular molecular lines that radio astronomers can study. Strong maser action was first detected in OH (at 1.6 GHz) and water (at 22 GHz) in star-forming regions, but with improvements in mm and submm-wave technology, and improved laboratory data, many new maser transitions are being identified. For methanol alone over 20 maser transitions have been identified in star-forming regions. This review summarizes recent observational developments. Masers provide the most readily detectable indicators of the formation of massive young stars, and offer our best prospect for making a complete census of starforming regions in the Galaxy. Using radio interferometers the structure of the regions can be probed on angular scales of 1 milliarcsecond. The use of masers as probes of the physical conditions in these regions is discussed.     

Equilibrium temperatures of interstellar iron grains

Because of the relatively low number densities found in typical interstellar clouds, molecules observed there must be produced by a combination of both two-body gas-phase reactions and surface reactions. The latter type includes various catalytic reactions, such as the formation of H₂ on transition metal grains. These reactions are very temperature dependent, the grain temperature appearing in the exponential of the rate equations. Because of the small heat capacities of the grains due to their small sizes, they may be subject to considerable fluctuations in temperature. This problem is examined for iron grains and found to be minimal for sizes greater than 100 Å. Steady-state equilibrium temperatures are then calculated for a size distribution of iron particles ranging from 10³ to 10⁹ atoms per grain by a refined method of an earlier work by one of us (RGT). The results are that iron grain temperatures are significantly greater than those of dielectric grains of comparable size in the same radiation field.     

星际E型CH3CN与H2的碰撞跃迁速率系数的理论计算

继本文作者对星际Ａ型ＣＨ３ＣＮ与Ｈ２含超精细能级的碰撞过程的研究之后，又计算了星际分子云条件下Ｅ型ＣＨ３ＣＮ与Ｈ２的碰撞跃迁速率系数。为研究分子云与恒星形成区的物理、化学性质提供了有用的基础分子数据。     

Organic synthesis in the coma of Comet Hale–Bopp?

Several organic molecules have now been detected in the coma of Hale–Bopp. These species may either emanate from the nucleus, or, as has been suggested by Bockelée–Morvan et al., could be synthesized in the coma. We have modelled the gas phase chemistry which occurred in the coma of Hale–Bopp, concentrating on the observed organic molecules HCOOH, HCOOCH₃, HC₃N and CH₃CN. We find that gas phase chemical reactions are unable to synthesize the observed abundances of these molecules, so all these species are most probably present in the nuclear ice. We briefly discuss the implications of this result for the connection between cometary and interstellar ices.     

Observations of chemical processing in the circumstellar environment

High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NGC 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.     

Solar System Processes Underlying Planetary Formation, Geodynamics, and the Georeactor

Only three processes, operant during the formation of the Solar System, are responsible for the diversity of matter in the Solar System and are directly responsible for planetary internal-structures, including planetocentric nuclear fission reactors, and for dynamical processes, including and especially, geodynamics. These processes are: (i) Low-pressure, low-temperature condensation from solar matter in the remote reaches of the Solar System or in the interstellar medium; (ii) High-pressure, high-temperature condensation from solar matter associated with planetary-formation by raining out from the interiors of giant-gaseous protoplanets, and; (iii) Stripping of the primordial volatile components from the inner portion of the Solar System by super-intense solar wind associated with T-Tauri phase mass-ejections, presumably during the thermonuclear ignition of the Sun. As described herein, these processes lead logically, in a causally related manner, to a coherent vision of planetary formation with profound implications including, but not limited to, (a) Earth formation as a giant gaseous Jupiter-like planet with vast amounts of stored energy of protoplanetary compression in its rock-plus-alloy kernel; (b) Removal of approximately 300 Earth-masses of primordial volatile gases from the Earth, which began Earth’s decompression process, making available the stored energy of protoplanetary compression for driving geodynamic processes, which I have described by the new whole-Earth decompression dynamics and which is responsible for emplacing heat at the mantle-crust-interface at the base of the crust through the process I have described, called mantle decompression thermal-tsunami; and, (c) Uranium accumulations at the planetary centers capable of self-sustained nuclear fission chain reactions.     

Interstellar catalysis

Since gas-phase reactions alone cannot account for the observed abundances of H₂ in the typical interstellar cloud, one or more surface reactions are probably involved. Of the three possible candidates, only the catalytic production of H₂ on transition metal grains is supported by laboratory evidence. Using the rate equations developed in a previous paper for this process, the steady-state equilibrium abundances of H, H₂,e ^–, H⁺, H^–, H₂ ⁺, and H₃ ⁺ are calculated for large (r>10 pcs;M10² M ), tenuous (n=10²–10⁴ cm^–3) hydrogen dust clouds under a wide variety of conditions. In addition to the four rate equations involved in the catalytic reactions, 18 gas-phase and one additional surface reaction—the physical adsorption of H-atoms on cold, dielectric surfaces and their subsequent recombination and desorption as H₂ molecules—are included in the calculations. It is found that metal grains can produce as much interstellar H₂ as the best physical adsorption mechanism under optimum conditions if the extinction in the visible is less than 5^m.0. The three critical parameters for efficient catalysis (activation energy of desorption, grain temperature, and the number density of available sites) are examined, and it is shown that catalytic reactions are efficient producers of H₂ under all but the most unfavorable conditions.