Kinetic Monte Carlo method for simulating astrochemical kinetics: Hydrogen chemistry in diffuse clouds

We perform numerical simulations of the molecular hydrogen production on the surface of interstellar dust grains and its dissociation by the ultraviolet background in conditions typical for the interstellar medium. The kinetic version of the Monte Carlo method is used for the modeling of the catalytic chemical reactions on the surface of the dust fraction and in the surrounding medium. Our simulations show the importance of the interstellar dust particles for hydrogen chemistry in diffuse molecular clouds.     

Model for surface reactions on interstellar grains — A numerical study

A model of the formation of molecules by surface reactions on interstellar grains is described and assessed numerically. The model predicts that for the molecules—other than H₂-likely to be important in the interstellar medium, the formation rates by surface reactions are insensitive to the nature of the surface. The formation rates have magnitudes which are significant when compared with other routes. The model also describes H₂ formation in high density clouds and shows it to be parameter dependent.     

The chemistry of interstellar nitrogen

A fairly complete but limited set of gas phase reactions involving nitrogen-bearing molecules is linked to a simple model of grain surface reactions. Calculations are performed attempting to simulate the nitrogen chemistry in interstellar clouds of low and high density. While it appears probable that grain surface reactions contribute to the chemistry in both régimes, conclusive evidence awaits observational and theoretical developments.     

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.     

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.     

Large interstellar molecules

We propose that photocycloaddition reactions in molecular complexes in normal interstellar clouds will create unusually large molecules. These may be sufficiently radiation stable to be circulated with the interstellar gas, and so provide convenient nucleation centres for growth of loosely bound grains in dark regions.     

Detection of interstellar hydrogen sulfide in cold, dark clouds

We have detected interstellar hydrogen sulfide (H2S) toward the cold, dark clouds L134N and TMC 1. We derive total column densities of approximately 2.6 x 10(13) cm-2 and approximately 7.0 x 10(12) cm-2 at the SO peak of L134N and at the NH3 peak of TMC 1, respectively. Since the expected gas phase reactions leading to the formation of H2S are thought to be endothermic, grain surface reactions may play a major role in the synthesis of this species in cold, dark clouds. If the carbon abundance is high and grain surface reactions are the dominant formation route, H2CS would be expected to form instead of H2S, and the abundances of H2CS have been observed to be high where those of H2S are low in L134N and TMC 1.     

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.     

Formation of complex chemical species in astrochemistry (a review)

In recent years, a rapid growth in a new area of space studies??astrochemistry??has been observed. Its subject is the chemical evolution and chemical diversity of interstellar matter. Molecules yield unique information concerning physical conditions in the interstellar medium and, in particular, in the star-formation regions, through spectral observations of the matter in the gas-phase and dust fractions via rotational and vibrational transitions of interstellar molecules. Moreover, an understanding of the chemistry of molecules can tell us about the lifetime and history of the observed objects. Such an understanding, however, requires detailed chemical knowledge of the gas-phase reactions and grain-surface chemical processes that very often take place under rather exotic conditions strongly differing from those for chemical reactions in the laboratory. Note that the interests of chemists and astronomers in this new area are different: chemists are more likely to be interested in chemical diversity throughout the Universe, whereas astronomers are more likely to use molecules as probes of physical processes.     

Silica grain catalysis of methanol formation

The specific catalytic effect of a silica grain on the formation of methanol via the sequential addition of H atoms to CO adsorbed on the surface is investigated. A negatively charged defect on a siliceous edingtonite surface is found to reduce the gas phase barriers for the H + CO_ads and H + H₂C=O_ads reactions by 770 and 399 K, respectively, when compared to the same reactions in the gas phase. The catalytic effect of negatively charged surface sites could also be applicable to the hydrogenation of other adsorbed unsaturated species. However, the activation energies on the surface defect are still too large (1150 and 2230 K) for CH₃OH to form efficiently at 10–20 K in the interstellar medium via a classical mechanism. It is therefore suggested that quantum mechanical tunnelling through the activation barrier is required for these hydrogen addition reactions to proceed at such temperatures. The calculations show that because the adsorption energies of CO and H₂C=O on the negatively charged defect are substantial, CH₃OH may form efficiently during the warm-up period in star-forming regions.     

Hydrogen isotopic substitution of solid methylamine through atomic surface reactions at low temperatures: A potential contribution to the D/H ratio of methylamine in molecular clouds

We experimentally studied hydrogen (H)–deuterium (D) substitution reactions of solid methylamine (CH₃NH₂) under astrophysically relevant conditions. We also calculated the potential energy surface for the H–D substitution reactions of methylamine isotopologues using quantum chemical methods. Despite the relatively large energy barrier of more than 18 kJ mol^?1, CH₃NH₂ reacted with D atoms to yield deuterated methylamines at 10 K, suggesting that the H–D substitution reaction proceeds through quantum tunneling. Deuterated methylamines reacted with H atoms as well. On the basis of present results, we propose that methylamine has potential for D enrichment through atomic surface reactions on interstellar grains at very low temperatures in molecular clouds. D enrichment would occur in particular in the methyl group of methylamine.     

Origin of the diffuse interstellar absorption bands

The influence of crystal structure and surface stresses on the spectrum of small interstellar particles has been investigated. Surface effects are predicted to result in the occurrence of pairs of features in the discrete absorption spectrum of interstellar dust. A simple relationship between the energy separation between lines of these pairs and their widths is derived which is tested against recent observational data on the diffuse interstellar band spectrum. Thirty of the diffuse bands can be accounted for on this basis by assuming that interstellar dust consists of a mixture of components of differing chemical composition.     

The possibility of nitrogen isotopic fractionation in interstellar clouds

The possibility of nitrogen isotopic fractionation owing to ion–molecule exchange reactions involving the most abundant N-containing species in dense interstellar clouds has been explored. We find that exchange reactions between N atoms and N-containing ions have most influence on the fractionation, although the extent of fractionation is too small to be readily detectable.     

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.     

Silicon chemistry in dense clouds

The equilibrium chemistry of silicon in dense interstellar clouds is discussed in terms of both gas phase and grain surface reactions. Unless the metal depletion is very large, the gas phase scheme tends to over-produce SiO and/or SiS when compared to the observations of Sgr B2. The scheme also predicts SiC to be an abundant form of silicon. There is a great need for relevant laboratory data on the reactions used here—of the 35 rate coefficients adopted in the scheme, only three have been measured in the laboratory. Reactions between positively charged gas phase ions and small grains can lead to the formation of SiO and SiS. This type of reaction seems to offer a simple explanation for the observed differences between sulphur and silicon chemistry in dense clouds.     

Probing the surfaces of interstellar dust grains: the adsorption of CO at bare grain surfaces

A solid-state feature was detected at around 2175 cm⁻¹ towards 30 embedded young stellar objects in spectra obtained using the Infrared Spectrometer and Array Camera at the European Southern Observatory Very Large Telescope. We present results from laboratory studies of CO adsorbed at the surface of zeolite wafers, where absorption bands were detected at 2177 and 2168 cm⁻¹ (corresponding to CO chemisorbed at the zeolite surface) and 2130 cm⁻¹ (corresponding to CO physisorbed at the zeolite surface), providing an excellent match to the observational data. We propose that the main carrier of the 2175-band is CO chemisorbed at bare surfaces of dust grains in the interstellar medium. This result provides the first direct evidence that gas–surface interactions do not have to result in the formation of ice mantles on interstellar dust. The strength of the 2175-band is estimated to be  ∼4 × 10⁻¹⁹ cm  molecule⁻¹. The abundance of CO adsorbed at bare grain surfaces ranges from 0.06 to 0.16 relative to H₂O ice, which is, at most, half of the abundance (relative to H₂O ice) of CO residing in H₂O-dominated ice environments. These findings imply that interstellar grains have a large (catalytically active) surface area, providing a refuge for interstellar species. Consequently, the potential exists for heterogeneous chemistry to occur involving CO molecules in unique surface chemistry pathways not currently considered in gas grain models of the interstellar medium.     

Interstellar water and interstellar ice

There are two ways that water ice can form in the interstellar medium: H₂O molecules can form in the gas phase and then freeze out onto dust grain surfaces, or O and OH can be converted at the surfaces of grains to form H₂O, which is then retained. Bergin et al. (1998) have recently shown that shocks passing through interstellar clouds sufficiently frequently can make the first method effective. However, we present results from a similar chemical model which indicate that this requires significant optical shielding because of the high ionization fraction in regions exposedto a high UV flux. We deduce, therefore, that grain surface reactions probably represent the main source of H₂O ice on lines of sight with visual extinction up to about 6 magnitudes to an embedded source or 12 magnitudes to a background object. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Chemical effects of irregular interstellar oxide grains

The importance of chemically-active geometrical surface sites on the surfaces of interstellar oxide grains is discussed in terms of their catalytic behaviour in molecular formation. Surface features — such as steps and corners — are considered in detail, and the binding energies of the hydrogen atom and the proton at these sites are estimated. It appears likely that chemical effects of interstellar oxide grains are located not only at point defects discussed elsewhere, but also at these geometrical surface features. Adsorbed surface species, surface reaction schemes, and the possible effects of grain impurities are briefly considered.     

The rate of the reaction between C2H and C2H2 at interstellar temperatures

The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.