Reaction Networks for Interstellar Chemical Modelling: Improvements and Challenges

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes—ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination—is reviewed. Emphasis is placed on those key reactions that have been identified, by sensitivity analyses, as ‘crucial’ in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalyzed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.     

Chemical and Physical Processing of Presolar Materials in the Solar Nebula and the Implications for Preservation of Presolar Materials in Comets

Chemical and physical processes in the outer solar nebula are reviewed. It is argued that the outer nebula was a chemically active environment with UV photochemistry and ion-molecule chemistry in its low density regions and grain-catalyzed chemistry in Jovian protoplanetary subnebulae. Presolar material was altered to greater or lesser extent by these spatially and temporally variable processes, which mimic many features of interstellar chemistry. Experiments, models, and observations are recommended to address the questions of presolar versus nebular dominance in the outer solar nebula and of how to distinguish interstellar and nebular sources of cometary volatiles. This revised version was published online in June 2006 with corrections to the Cover Date.     

Spectroscopy Between the Stars

The emission and absorption spectra of interstellar molecules are reviewed with special consideration of recent observational and technical advances in the shorter submillimeter wave region of the electromagnetic spectrum. Single-dish observations have contributed in the past probably most of the information about the structure of interstellar molecular clouds. At present about 120 interstellar molecules have been identified in interstellar clouds and circumstellar envelopes, evidence of a rich and diversified chemistry. CO, the most abundant interstellar molecule and other diatomic molecules and radicals are found throughout molecular clouds, whereas the more complex molecules are found in high-density cores, which are often the sites of active star formation. These locations represent prime targets for the search for larger molecules, such as glycine. The ignition of young stars is accompanied by strong heating of the surrounding material by radiation and/or shocks, leading to photoevaporation of molecules depleted on dust grains driving a "hot core" chemistry, traceable by its rich organic chemistry and its prevailing high excitation conditions (up to about 2000 cm^-1). However, in the list of detected interstellar molecules many simple hydrides are still missing, e.g. SH, PH, PH₂, etc., which constitute the building blocks for larger molecules. With the technological opening of the terahertz region (ν ∼1 THz corresponds to λ ∼0.3 mm) to both laboratory and interstellar spectroscopy, great scientific advances are to be expected. Amongst these will be the direct detection of the lowest rotational transitions of the light hydrides, the low energy bending vibrations of larger (linear) molecules, and possibly the ring-puckering motion of larger ring molecules such as the polycyclic (multiring) aromatic hydrocarbons. This revised version was published online in June 2006 with corrections to the Cover Date.     

Dust Properties in the Local Interstellar Medium

Ulysses measurements yield reliable in-situdetection of large dust particles which stem from the interstellar medium (ISM) and which are not observed in interstellar extinction data. Both current models of large grains in the ISM: core-mantle grains as well as composite grains, are in agreement with dust properties implied by the Ulysses results. However, the size of particles detected by Ulysses still exceeds the size of the large grains that are predicted for the ISM. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cosmic-ray acceleration and transport,and diffuse galactic γ-ray emission

Cosmic-ray acceleration and transport is considered from the point of view of application to diffuse galactic -ray sources. As an introduction we review several source models, in particular supernovae exploding inside or near large interstellar clouds. The complex problem of cosmic ray transport in random electromagnetic fields is reduced to three cases which should be sufficient for practical purposes. As far as diffusive acceleration is concerned, apart from reviewing the basic physical principles, we point out the relation between shock acceleration and 2nd order Fermi acceleration, and the relative importance of the two processes around interstellar shock waves. For -ray source models the interaction of cosmic rays with dense clouds assumes great importance. Past discussions had been confined to static interactions of clouds with the ambient medium in the sense that no large scale mass motions in the ambient interstellar medium were considered. The well-known result then is that down to some tens of MeV or less, cosmic-ray nucleons should freely penetrate molecular clouds of typical masses and sizes. The self-exclusion of very low energy nucleons however may affect electron transport with consequences for the Bremsstrahlung -luminosity of such clouds.In this paper we consider also the dynamical interaction of dense clouds with a surrounding hot interstellar medium. Through cloud evaporation and accretion there exist mass flows in the cloud surroundings. We argue that in the case of (small) cloud evaporation the galactic cosmic rays will be essentially excluded from the clouds. The dynamic effects of cosmic rays on the flow should be minor in this case. For the opposite case of gas accretion onto (large) clouds, cosmic-ray effects on the flow will in general be large, limiting the cosmic-ray compression inside the cloud to dynamic pressure equilibrium. This should have a number of interesting and new consequences for -ray astronomy. A first, qualitative discussion is given in the last section.Proceedings of the XVIII General Assembly of the IAU: Galactic Astrophysics and Gamma-Ray Astronomy, held at Patras, Greece, 19 August 1982.     

Isotopic Fractionation by Ion-Molecule Reactions

Isotopic fractionation in interstellar clouds can occur by ion-molecule reactions at low temperatures. The major effect is not kinetic but thermodynamic in origin in that it arises from the difference in rate coefficients between forward and backward directions in reactions which exchange isotopic atoms. In this article, we concentrate on deuterium fractionation in interstellar clouds; this effect enhances the relative abundances of deuterated isotopomers to their normal counterparts by up to four orders of magnitude as compared with the basic D/H elemental abundance ratio. We also discuss the fractionation of ¹⁵N and ¹³C. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Composition of Interstellar Molecular Clouds

We consider four aspects of interstellar chemistry for comparison with comets: molecular abundances in general, relative abundances of isomers (specifically, HCN and HNC), ortho/para ratios for molecules, and isotopic fractionation, particularly for the ratio hydrogen/deuterium. Since the environment in which the solar system formed is not well constrained, we consider both isolated dark clouds where low mass stars may form and the "hot cores" that are the sites of high mass star formation. Attention is concentrated on the gas phase, since the grains are considered elsewhere in this volume. This revised version was published online in June 2006 with corrections to the Cover Date.     

Deuterium Fractionation in Interstellar Clouds

This paper reviews the chemical processes responsible for fractionating deuterium in interstellar molecules. I show that this process is intrinsically a low temperature phenomenon and discuss how the degree of enhancement of the deuterium content of molecules is related to the physical conditions, particularly abundances, in molecular clouds. If significant amounts of abundant species, such as CO, are frozen out on to interstellar dust grains, the resulting enhancement in H₂D⁺ can result in its abundance being greater than that of H ₃ ⁺ at 10K. Transfer of the deuteron from H₂D⁺ can then lead to the efficient formation of multiply deuterated species, such as NHD₂ and ND₃. Fractionation can also occur in grain surface reactions and some simple models are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Formation and Processing of Organics in the Early Solar System

Until pristine samples can be returned from cometary nuclei, primitive meteorites represent our best source of information about organic chemistry in the early solar system. However, this material has been affected by secondary processing on asteroidal parent bodies which probably did not affect the material now present in cometary nuclei. Production of meteoritic organic matter apparently involved the following sequence of events: Molecule formation by a variety of reaction pathways in dense interstellar clouds; Condensation of those molecules onto refractory interstellar grains; Irradiation of organic-rich interstellar-grain mantles producing a range of molecular fragments and free radicals; Inclusion of those interstellar grains into the protosolar nebula with probable heating of at least some grain mantles during passage through the shock wave bounding the solar accretion disc; Agglomeration of residual interstellar grains and locally produced nebular condensates into asteroid-sized planetesimals; Heating of planetesimals by decay of extinct radionuclides; Melting of ice to produce liquid water within asteroidal bodies; Reaction of interstellar molecules, fragments and radicals with each other and with the aqueous environment, possibly catalysed by mineral grains; Loss of water and other volatiles to space yielding a partially hydrated lithology containing a complex suite of organic molecules; Heating of some of this organic matter to generate a kerogen-like complex; Mixing of heated and unheated material to yield the meteoritic material now observed. Properties of meteoritic organic matter believed to be consistent with this scenario include: Systematic decrease of abundance with increasing C number in homologous series of characterisable molecules; Complete structural diversity within homologous series; Predominance of branched-chain isomers; Considerable isotopic variability among characterisable molecules and within kerogen-like material; Substantial deuterium enrichment in all organic fractions; Some fractions significantly enriched in nitrogen-15; Modest excesses of L-enantiomers in some racemisation-resistant molecules but no general enantiomeric preference. Despite much speculation about the possible role of Fischer-Tropsch catalytic hydrogenation of CO in production of organic molecules in the solar nebula, no convincing evidence for such material has been found in meteorites. A similarity between some meteoritic organics and those produced by Miller-Urey discharge synthesis may reflect involvement of common intermediates rather than the operation of electric discharges in the early solar system. Meteoritic organic matter constitutes a useful, but not exact, guide to what we shall find with in situ analytical and sample-return missions to cometary nuclei. This revised version was published online in June 2006 with corrections to the Cover Date.     

The Ice Survey Opportunity of ISO

The instruments on board the Infrared Space Observatory have for the first time allowed a complete low (PHOT, CVF) to medium resolution (SWS) spectroscopic harvest, from 2.5 to 45 μm, of interstellar dust. Amongst the detected solids present in starless molecular clouds surrounding recently born stellar and still embedded objects or products of the chemistry in some mass loss envelopes, the so-called “ice mantles” are of specific interest. They represent an interface between the very refractory carbonaceous and silicates materials that built the first grains with the rich chemistry taking place in the gas phase. Molecules condense, react on ices, are subjected to UV and cosmic ray irradiation at low temperatures, participating efficiently to the evolution toward more complex molecules, being in constant interaction in an ice layer. They also play an important role in the radiative transfer of molecular clouds and strongly affect the gas phase chemistry. ISO results shed light on many other species than H₂O ice. The detection of these van der Waal's solids is mainly performed in absorption. Each ice feature observed by ISO spectrometer is an important species, with abundance in the 10⁻⁴–10⁻⁷ range with respect to H₂. Such high abundances represent a substantial reservoir of matter that, once released later on, replenishes the gas phase and feeds the ladder of molecular complexity. Medium resolution spectroscopy also offers the opportunity to look at individual line profiles of the ice features, and therefore to progressively reveal the interactions taking place in the mantles. This article will give a view on selected results to avoid to overlap with the numerous reviews the reader is invited to consult (e.g. van Dishoeck, in press; Gibb et al., 2004.). Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, The Netherlands, and the United Kingdom), and with the participation of ISAS and NASA.     

D/H and Nearby Interstellar Cloud Structures

Analysis of UV spectra obtained with the HST, FUSE and other satellites provides a new understanding of the deuterium abundance in the local region of the galactic disk. The wide range of gas-phase D/H measurements obtained outside of the Local Bubble can now be explained as due to different amounts of deuterium depletion on carbonaceous grains. The total D/H ratio including deuterium in the gas and dust phases is at least 23 parts per million of hydrogen, which is providing a challenge to models of galactic chemical evolution. Analysis of HST and ground-based spectra of many lines of sight to stars within the Local Bubble have identified interstellar velocity components that are consistent with more than 15 velocity vectors. We have identified the structures of 15 nearby warm interstellar clouds on the basis of these velocity vectors and common temperatures and depletions. We estimate the distances and masses of these clouds and compare their locations with cold interstellar clouds.     

Deuterium in Molecules of the Interstellar Medium

Deuterated molecules are detected both in interstellar translucent clouds and in cold dark clouds, as well as in star forming regions. We review the recent observational studies of deuterated molecules ranging from the VUV to the millimeter wavelength range. We outline some sources of uncertainties on the deuterium fractionation and on the subsequent derivation of the elemental deuterium to hydrogen ratio. Steady state versus time dependent models are discussed and the role of initial conditions is emphasized. This revised version was published online in August 2006 with corrections to the Cover Date.     

Magnetic Fields in the Multiphase Interstellar Medium

We discuss the interstellar magnetic field and its measurement in the different phases of the interstellar medium. The measurement techniques include Faraday rotation, Zeeman splitting, linear polarization from aligned dust grains, and the Chandrasekhar-Fermi method. The phases include the classical ones: molecular clouds, the Cold and Warm Neutral Media, the Warm and Hot Ionized Media. We also include a less well-known phase, the Warm Partially Ionized Medium, which can be surprisingly prominent in Faraday rotation.     

The Cool Interstellar Medium

Infrared spectroscopy and photometry with ISO covering most of the emission range of the interstellar medium has led to important progress in the understanding of the physics and chemistry of the gas, the nature and evolution of the dust grains and also the coupling between the gas and the grains. We review here the ISO results on the cool and low-excitation regions of the interstellar medium, where T _gas≲ 500 K, n _H∼ 100–10⁵ cm⁻³ and the electron density is a few 10⁻⁴. JEL codes: D24, L60, 047 Based on observations with ISO, an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, The Netherlands, and the United Kingdom), and with the participation of ISAS and NASA.     

Reservoir for Comet Material: Circumstellar Grains

Primitive meteorites and interplanetary dust particles contain small quantities of dust grains with highly anomalous isotopic compositions. These grains formed in the winds of evolved stars and in the ejecta of stellar explosions, i.e., they represent a sample of circumstellar grains that can be analyzed with high precision in the laboratory. Such studies have provided a wealth of information on stellar evolution and nucleosynthesis, Galactic chemical evolution, grain growth in stellar environments, interstellar chemistry, and the inventory of stars that contributed dust to the Solar System. Among the identified circumstellar grains in primitive solar system matter are diamond, graphite, silicon carbide, silicon nitride, oxides, and silicates. Circumstellar grains have also been found in cometary matter. To date the available information on circumstellar grains in comets is limited, but extended studies of matter returned by the Stardust mission may help to overcome the existing gaps.     

Evolution of the Protosolar Nebula and Formation of the Giant Planets

The formation of planetary systems is intimately tied to the question of the evolution of the gas and solid material in the early nebula. Current models of evolution of circumstellar disks are reviewed here with emphasis on the so-called “alpha models” in which angular momentum is transported outward by turbulent viscosity, parameterized by an dimensionless parameter α. A simple 1D model of protoplanetary disks that includes gas and embedded particles is used to introduce key questions on planetesimal formation. This model includes the aerodynamic properties of solid ice and rock grains to calculate their migration and growth. We show that the evolution of the nebula and migration and growth of its solids proceed on timescales that are generally not much longer than the timescale necessary to fully form the star-disk system from the molecular cloud. Contrary to a widely used approach, planet formation therefore can neither be studied in a static nebula nor in a nebula evolving from an arbitrary initial condition. We propose a simple approach to both account for sedimentation from the molecular cloud onto the disk, disk evolution and migration of solids. Giant planets have key roles in the history of the forming Solar System: they formed relatively early, when a significant amount of hydrogen and helium were still present in the nebula, and have a mass that is a sizable fraction of the disk mass at any given time. Their composition is also of interest because when compared to the solar composition, their enrichment in elements other than hydrogen and helium is a witness of sorting processes that occured in the protosolar nebula. We review likely scenarios capable of explaining both the presence of central dense cores in Jupiter, Saturn, Uranus and Neptune and their global composition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cometary Refractory Grains: Interstellar and Nebular Sources

Comets are heterogeneous mixtures of interstellar and nebular materials. The degree of mixing of interstellar sources and nebular sources at different nuclear size scales holds the promise of revealing how cometary particles, cometesimals, and cometary nuclei accreted. We can ascribe cometary materials to interstellar and nebular sources and see how comets probe planet-forming process in our protoplanetary disk. Comets and cometary IDPs contain carbonaceous matter that appears to be either similar to poorly-graphitized (amorphous) carbon, a likely ISM source, or highly labile complex organics, with possible ISM or outer disk heritage. The oxygen fugacity of the solar nebula depends on the dynamical interplay between the inward migration of carbon-rich grains and of icy (water-rich) grains. Inside the water dissociation line, OH^? reacts with carbon to form CO or CO₂, consuming available oxygen and contributing to the canonical low oxygen fugacity. Alternatively, the influx of water vapor and/or oxygen rich dust grains from outer (cooler) disk regions can raise the oxygen fugacity. Low oxygen fugacity of the canonical solar nebula favors the condensation of Mg-rich crystalline silicates and Fe-metal, or the annealing of Fe-Mg amorphous silicates into Mg-rich crystals and Fe-metal via Fe-reduction. High oxygen fugacity nebular conditions favors the condensation of Fe-bearing to Fe-rich crystalline silicates. In the ISM, Fe-Mg amorphous silicates are prevalent, in stark contrast to Mg-rich crystalline silicates that are rare. Hence, cometary Mg-rich crystalline silicates formed in the hot, inner regions of the canonical solar nebula and they are the touchstone for models of the outward radial transport of nebular grains to the comet-forming zone. Stardust samples are dominated by Mg-rich crystalline silicates but also contain abundant Fe-bearing and Fe-rich crystalline silicates that are too large (?0.1 μm) to be annealed Fe-Mg amorphous silicates. By comparison with asteroids, the Stardust Fe-bearing and Fe-rich crystalline silicates suggests partial aqueous alteration in comet nuclei. However, aqueous alteration transforms Fe-rich olivine to phyllosilicates before Mg-rich olivine, and Stardust has Mg-rich and Fe-rich olivine and no phyllosilicates. Hence, we look to a nebular source for the moderately Fe-rich to nearly pure-Fe crystalline silicates. Primitive matrices have Mg-Fe silicates but no phyllosilicates, supporting the idea that Mg-Fe silicates but not phyllosilicates are products of water-rich shocks. Chondrule-formation is a late stage process in our protoplanetary disk. Stardust samples show comet 81P/Wild 2 formed at least as late to incorporate a few chondrules, requiring radial transport of chondrules out to perhaps >20 AU. By similar radial transport mechanisms, collisional fragments of aqueously altered asteroids, in particular achondrites that formed earlier than chondrules, might reach the comet-forming zones. However, Stardust samples do not have phyllosilicates and chondrules are rare. Hence, the nebular refractory grains in comet 81P/Wild 2, as well as other comets, appear to be pre-accretionary with respect to asteroid parent bodies. By discussing nebular pathways for the formation of Fe-rich crystalline silicates, and also phyllosilicates and carbonates, we put forth the view that comets contain both the interstellar ingredients for and the products of nebular transmutation.     

Heliospheric and Interstellar Phenomena Deduced From Pickup ion Observations

Pickup ions, created by ionization of slow moving atoms and molecules well inside the heliosphere, provide us with a new tool to probe remote regions in and beyond the heliosphere and to study injection and acceleration processes in the solar wind. Comprehensive and continuous measurements of H, He, C, N, O, Ne and other pickup ions, especially with the Solar Wind Ion Composition Spectrometer (SWICS) on both Ulysses and ACE, have given us a wealth of data that have been used to infer chemical and physical properties of the local interstellar cloud. With SWICS on Ulysses we discovered a new population of pickup ions, produced from atomic and molecular sources deep inside the heliosphere. The velocity distributions and composition of these “inner source” pickup ions are distinctly different from those of interstellar pickup ions, showing effects of strong adiabatic cooling, and a composition resembling that of the solar wind. Strong cooling indicates that the source of these pickup ions lies close to the Sun. The similarity of composition of inner source heavy ions to that of the solar wind implies that the dominant production mechanism for these pickup ions involves the absorption and re-emission of solar wind from interplanetary dust grains. While interstellar pickup ions are the seed population of the main Anomalous Cosmic Rays (ACRs), inner source pickup ions may be an important source of the rarer ACRs such as C, Mg, Si, S, and Fe. We present new results and review previous work with an emphasis on characteristics of the local interstellar cloud and properties of the inner source. This revised version was published online in August 2006 with corrections to the Cover Date.     

The relevance of molecular observations to gamma-ray astronomy

The interaction of cosmic rays with interstellar clouds may produce some of the observed gamma-ray sources. The use of molecular observations to estimate the cloud masses, which are used to derive cosmic-ray fluxes, is reviewed. Molecular diagnostics of high cosmic-ray ionization rates are discussed, and a detailed application of those diagnostics is summarised and presented as evidence that second-order Fermi acceleration is important in old supernova remnants and can produce cosmic rays of too low energy to induce gamma-ray emission.Proceedings of the XVIII General Assembly of the IAU: Galactic Astrophysics and Gamma-Ray Astronomy, held at Patras, Greece, 19 August 1982.Royal Society Jaffé Donation Fellow.