New models of interstellar gas–grain chemistry – I. Surface diffusion rates

In recent years it has become evident that large differences can exist between model results of grain-surface chemistry obtained from a rate equation approach and from a Monte Carlo technique. This dichotomy has led to the development of a modified rate equation method, in which a key element is the artificial slowing down of the diffusion rate of surface hydrogen atoms. Recent laboratory research into the surface diffusion rate of atomic hydrogen suggests that atomic hydrogen moves more slowly on grains than heretofore assumed. This research appears to lessen the need for modifications to the rate equation method. Based on the new laboratory work, we have developed appropriate models of gas-phase and grain-surface chemistry in quiescent dense cloud cores to examine the chemical effects of slowing down the rate at which atomic H can scan over dust surfaces. Furthermore, we have investigated the effect of slowing down the rate at which all species can move over grain surfaces.     

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.     

New models of interstellar gas–grain chemistry – III. Solid CO2

Solid CO₂ is observed to be an abundant interstellar ice component towards both quiescent clouds and active star-forming regions. Our recent models of gas–grain chemistry, appropriate for quiescent regions, severely underproduce solid CO₂ at the single assumed gas density and temperature. In this paper, we investigate the sensitivity of our model results to changes in these parameters. In addition, we examine how the nature of the grain surface affects the results and also consider the role of the key surface reaction between O and CO. We conclude that the observed high abundance of solid CO₂ can be reproduced at reasonable temperatures and densities by models with diffusive surface chemistry, provided that the diffusion of heavy species such as O occurs efficiently.     

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.     

Injection of molecules from the surfaces of grains into the gas phase chemistry of an expanding cloud

We present model results for the chemistry in an expanding cloud or clump in which molecules are injected into the gas phase from grain surfaces when the clump reaches a certain visual extinction A _v during the expansion. We consider separately injection at two different values of A _v, and include a representative large hydrocarbon, C₆H, and sulphur-bearing molecule, H₂SO₄, as well as H₂O and CO. We examine the abundances of certain molecules which have been observed in diffuse and translucent clouds, and compare the results obtained for these abundances with and without an injection during expansion. We also compare our results withpublished observations, and conclude that in most clouds an injection of molecules has occurred.     

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.     

Desorption processes and the deuterium fractionation in molecular clouds

Several processes have been suggested as ways of returning accreted grain mantles to the gas, thus preventing the total removal of molecules from the gas phase in dark quiescent clouds. We attempt to distinguish between them by considering not only the calculated gas-phase abundances, but also the ratio of the abundances of deuterated species to non-deuterated species. We find that the D/H ratio in molecules is relatively model-independent, but that desorption due to the formation of H₂ on grains gives the best overall agreement with the observations.     

Structure and chemistry in the hot molecular core G34.3+0.15

New multifrequency spatial and spectral studies of the hot molecular core associated with the ultracompact HII region G34.3+0.15 have demonstrated an extremely rich chemistry in this archetypal hot core and revealed differing spatial structure between certain species which may be a dynamical effect of chemical evolution. The structure of the hot core has been studied with the JCMT in the high excitation J=19-18 and J=18-17 lines of CH₃CN and with the Nobeyama Millimetre Array at 4 arc resolution in the J=6-5 transition. Comparison with a VLA NH₃(3,3) map shows a displacement between peak emission in the two chemical species which is consistent with chemical processing on a time scale comparable to the dynamical time scale of 10⁵ yrs.A 330-360 GHz spectral survey of the hot core with the JCMT has detected 358 spectral lines from at least 46 distinct chemical species, including many typical of shocked chemistry while other species indicate abundances that reflect the chemistry of a previous cold phase. The first unambiguous detection of ethanol in hot gas has been made. Observations of 14 rotational transitions of this molecule yield a temperature of 125 K and column density 2×10¹⁵ cm^–2. This large abundance cannot be made by purely gas-phase processes and it is concluded that ethanol must have formed by grain surface chemistry.     

Observational Indicators of Formation Excitation of H2

Theoretical predictions by Farebrother et al. and Meijer et al. of rovibrational excitation probabilities in H₂ arising from formation by Eley-Rideal processes on a graphite surface are incorporated into a model of the chemistry and excitation of interstellar H₂. The model includes the usual radiative and collisional pumping of H₂ rotational and vibrational states, in addition to the formation processes. Predictions are made for HH₂ rovibrational emission line intensities for representative points in diffuse and in dark interstellar clouds. We find that – if all the interstellar HH₂ is formed by this Eley-Rideal process – then the consequences of formation pumping, as distinct from collisional and radiative pumping, should be clearly evident in both cases. In particular, we predict a clear spectral signature of this direct HH₂ formation process on graphite, distinct from radiative and collisional pumping; this signature should be evident in both diffuse and dark clouds; but the emissivity for dark clouds is predicted to be some 500 times greater than that in diffuse clouds in which the dense material may be embedded. An observational search for this signature in two dark cloud sources was made, but a preliminary analysis of the data did not yield a detection. The implications of and possible reasons for this preliminary conclusion are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

New approaches to the modelling of surface chemistry on interstellar grains

In recent years, the need to replace rate equations for studying grain-surface chemistry in the modelling of interstellar clouds has become apparent. In this article, we discuss the three new replacement methods that have been suggested to date, and contrast their relative strengths and weaknesses. This revised version was published online in July 2006 with corrections to the Cover Date.     

H3+ in diffuse interstellar gas

A model is constructed of the material in front of the star Cygnus OB2 no. 12 in which dense cores are embedded in diffuse clumps of gas. The model reproduces the measured abundances of C₂ and CO, and predicts a column density of 910¹⁰ cm² for HCO⁺.     

HE 1127–1304: the largest radio quasar

By considering the propagation of low-amplitude magnetohydrodynamic waves in partially ionized plasmas, it is shown that the ion-neutral drift (ambipolar diffusion) induced by the waves can have specific effects on the molecular chemistry of cold material. The chemistry occurring in gas swept by Alfvén waves is described and it is shown that this leads to spatial variations in the deuterium fractionation ratios of, for example, HCO⁺ and N₂H⁺, on spatial scales of a few hundredths of a parsec, depending upon the fractional ionization of the ambient medium. The possibility of detecting interstellar Alfvén waves by molecular spectroscopy and their effect of producing small-scale chemical abundance gradients in molecular clouds are briefly discussed.     

On the detection of interstellar homonuclear diatomic molecules

The pure rotational spectrum of homonuclear diatomic molecules in the interstellar medium is strongly forbidden, and no such spectrum has been detected. In regions of high excitation, vibrational emission may occur, as is widely detected in the case of H₂ in interstellar shocks and photon-dominated regions. However, it is of considerable interest to know the abundance of homonuclear diatomics in quiescent regions. We propose that vibrational emission from homonuclear diatomic molecules in cold clouds may be detectable, where the excitation is mainly through collisions with non-thermal electrons arising from the cosmic-ray ionization of H₂. As an example, we estimate the intensity of emission from N₂ in cold, dark interstellar clouds. We show that such emission is at the limit of detectability with current technology. Other excitation mechanisms may also contribute and enhance this emission.