Chemically driven desorption of CO from icy grains in dark clouds

The chemical desorption of an adsorbed CO molecule in the vicinity of H₂-forming sites on cosmic dust grains in cold dense clouds is investigated theoretically, mainly using a model based on a classical molecular dynamics computational simulation. As a model surface for icy mantles of dust grains, an amorphous water ice slab is generated at 10 K, and the first and the second H atoms are thrown on to the model surface to reproduce the recombination process of the two H atoms, H+H→H₂. Then, the time and space dependence of the local temperature increase of icy mantles caused by the release of H₂ formation energy in the vicinity of H₂-forming sites is examined. It is found that icy mantles are heated locally up to about 30 K in the surface region at R 4 Å and about 20 K at 4 R 6 Å, where R is the distance from the H₂-forming site. The critical temperature of CO desorption is estimated to be about 20–30 K under conditions in typical dense clouds, which might be seen to be comparable to the above result. However, the lifetime of local heating of icy mantles is found to be too short, compared with the time-scale of CO desorption (10¹³ s) and that for H₂ forming in the vicinity of an adsorbed CO molecule (more than 2×10¹³ s). Thus, it is found that the efficiency of chemical desorption of CO on a large dust grain is negligible. On the other hand, chemical desorption can occur on a small dust grain with size less than 20 Å.     

Measurements of the 44-μm band of H2O ice deposited on amorphous carbon and amorphous silicate substrates

We present 20–110 µm absorbance spectra of H₂O ice, deposited on amorphous carbon and silicate substrates, obtained over the 10–140 K temperature range. The measurements have been carried out in a manner that simulates the deposition, warming and cooling of H₂O ice mantles on interstellar and circumstellar grains. For H₂O ice films deposited on these substrates we find (i) similar 44-µm-band peak wavelength temperature dependences, (ii) no bandshape differences in the respective spectra, and (iii) a structural phase transition occurring between 120 and 130 K. In comparison with published data obtained using a polyethylene substrate, the 52-µm feature (the longitudinal optical mode) observed in our spectra is less prominent. This suggests the presence of material-dependent substrate effects that can alter the appearance of the H₂O far-infrared spectrum. The crystallization temperature of H₂O ice films deposited on our amorphous silicate substrate is significantly different from that reported by Moore et al. (1994) , who found crystallization temperatures down to < 20 K for ice also deposited on an amorphous silicate substrate. This is attributed to differences in the surface structures of the respective substrates. This may indicate that, at least in the context of laboratory measurements, substrate material composition is not as significant as substrate surface structure.     

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.     

Ice in the Southern Coalsack

To better understand the conditions under which ice mantles form on grains in molecular clouds, three globules in the Southern Coalsack have been searched for the presence of H₂O ice. Given the total lack of star formation in the Coalsack, it is an ideal site for studying unprocessed icy molecular mantles. In our sample of eight field stars lying behind the Coalsack we detect strong H₂O ice absorption in the lines of sight to two stars and possible weak absorption in four others. We estimate H₂O ice column densities or upper limits for these lines of sight. Compared to dark clouds such as Taurus, the Coalsack H₂O ice column densities are lower than expected given the quiescent nature of the Coalsack region. It is possible that the chemical evolution of the Coalsack may simply be at too early a stage for significant ice mantles to appear on the grains, except perhaps in the densest parts of some of the globules. Alternatively, the presence or absence of ice absorption may be related to the distribution of dust along each line of sight, specifically, the relative contributions of dense globules and a more extended diffuse component. For example, our observations are consistent with an ice threshold extinction similar to that observed in the Taurus dark cloud if extinction amounting to   A _V∼5  towards Globules 2 and 3 arises in the extended component. Globule 1 appears to have no extended component.     

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.     

Hydrated sulphuric acid in dense molecular clouds

We consider sulphur depletion in dense molecular clouds, and suggest hydrated sulphuric acid, H₂SO₄ ·  n H₂O, as a component of interstellar dust in icy mantles. We discuss the formation of hydrated sulphuric acid in collapsing clouds and its instability in heated regions in terms of the existing hot core models and observations. We also show that some features of the infrared spectrum of hydrated sulphuric acid have correspondence in the observed spectra of young stellar objects.     

Water in the near-infrared spectrum of comet 8P/Tuttle

High-resolution spectra of comet 8P/Tuttle were obtained in the frequency range 3449.0–3462.2 cm⁻¹ on 2008 January 3 ut using CGS4 with echelle grating on United Kingdom Infrared Telescope. In addition to observing solar pumped fluorescent lines of H₂O, the long integration time (152 min on target) enabled eight weaker H₂O features to be assigned, most of which had not previously been identified in cometary spectra. These transitions, which are from higher energy upper states, are similar in character to the so-called SH lines recorded in the post Deep Impact spectrum of comet Tempel 1. We have identified certain characteristics that these lines have in common, and which in addition to helping to define this new class of cometary line give some clues to the physical processes involved in their production. Finally, we derive an H₂O rotational temperature of     and a water production rate of  (1.4 ± 0.3) × 10²⁸  molecules s⁻¹.     

Dust coagulation in star formation with different metallicities

Dust grains coagulate into larger aggregates in dense gas. This changes their size distribution and possibly affects the thermal evolution of star-forming clouds. We here investigate dust coagulation in collapsing pre-stellar cores with different metallicities by considering the thermal motions of grains. We show that coagulation does occur even at low metallicity  ∼10⁻⁶ Z_⊙  . However, we also find (i) that the H₂ formation rate on dust grains is reduced only after the majority of H₂ is formed and (ii) that the dust opacity is modified only after the core becomes optically thick. Therefore, we conclude that the effects of dust coagulation can safely be neglected in discussing the temperature evolution of the pre-stellar cores for any metallicity as long as the grain motions are thermal.     

Cumulenic and heterocumulenic anions: potential interstellar species?

A recent theoretical investigation by Terzieva & Herbst of linear carbon chains, C _n where n  ≥ 6, in the interstellar medium has shown that these species can undergo efficient radiative association to form the corresponding anions. An experimental study by Barckholtz, Snow & Bierbaum of these anions has demonstrated that they do not react efficiently with molecular hydrogen, leading to the possibility of detectable abundances of cumulene-type anions in dense interstellar and circumstellar environments. Here we present a series of electronic structure calculations which examine possible anionic candidates for detection in these media, namely the anion analogues of the previously identified interstellar cumulenes C _n H and C _{n −1}CH₂ and heterocumulenes C _n O (where n  = 2–10). The extraordinary electron affinities calculated for these molecules suggest that efficient radiative electron attachment could occur, and the large dipole moments of these simple (generally) linear molecules point to the possibility of detection by radio astronomy.     

Radiative feedback from ionized gas

H₂ formation in metal-free gas occurs via the intermediate  H⁻  or  H⁺₂  ions. Destruction of these ions by photodissociation therefore serves to suppress  H₂  formation. In this paper, I highlight the fact that several processes that occur in ionized primordial gas produce photons energetic enough to photodissociate  H⁻  or  H⁺₂  and outline how to compute the photodissociation rates produced by a particular distribution of ionized gas. I also show that there are circumstances of interest, such as during the growth of H  ii regions around the first stars, in which this previously overlooked form of radiative feedback is of considerable importance.     

Desorption from interstellar ices

The desorption of molecular species from ice mantles back into the gas phase in molecular clouds results from a variety of very poorly understood processes. We have investigated three mechanisms: desorption resulting from H₂ formation on grains, direct cosmic ray heating and cosmic ray-induced photodesorption. Whilst qualitative differences exist between these processes (essentially deriving from the assumptions concerning the species selectivity of the desorption and the assumed threshold adsorption energies, E _t), all the three processes are found to be potentially very significant in dark cloud conditions. It is therefore important that all three mechanisms should be considered in studies of molecular clouds in which freeze-out and desorption are believed to be important.
Employing a chemical model of a typical static molecular core and using likely estimates for the quantum yields of the three processes, we find that desorption by H₂ formation probably dominates over the other two mechanisms. However, the physics of the desorption processes and the nature of the dust grains and ice mantles are very poorly constrained. We therefore conclude that the best approach is to set empirical constraints on the desorption, based on observed molecular depletions – rather than try to establish the desorption efficiencies from purely theoretical considerations. Applying this method to one such object (L16 89B) yields upper limits to the desorption efficiencies that are consistent with our understanding of these mechanisms.     

Interaction between the north-eastern boundary of Sgr A East and giant molecular clouds

We have detected the   v = 1 → 0 S(1) (λ= 2.1218 μm)  and   v = 2 → 1 S(1) (λ= 2.2477 μm)  lines of H₂ in the Galactic Centre, in a  90 × 27 arcsec²  region between the north-eastern boundary of the non-thermal source Sgr A East, and the giant molecular cloud (GMC)  M−0.02 − 0.07  . The detected  H₂ v = 1 → 0  S(1) emission has an intensity of  1.6–21 × 10⁻¹⁸ W m⁻² arcsec⁻²  and is present over most of the region. Along with the high intensity, the large linewidths  (FWHM = 40–70 km s⁻¹)  and the  H₂ v = 2 → 1 S(1)  to   v = 1 → 0 S(1)  line ratios (0.3–0.5) can be best explained by a combination of C-type shocks and fluorescence. The detection of shocked H₂ is clear evidence that Sgr A East is driving material into the surrounding adjacent cool molecular gas. The H₂ emission lines have two velocity components at ∼+50 and  ∼0 km s⁻¹  , which are also present in the NH₃(3, 3) emission mapped by McGary, Coil & Ho. This two-velocity structure can be explained if Sgr A East is driving C-type shocks into both the  GMC M−0.02 − 0.07  and the northern ridge of McGary et al.     

Formation of H2 on an olivine surface: a computational study

The formation of H₂ on a pristine olivine surface [forsterite (010)] is investigated computationally. Calculations show that the forsterite surface catalyzes H₂ formation by providing chemisorption sites for H atoms. The chemisorption route allows for stepwise release of the reaction exothermicity and stronger coupling to the surface, which increases the efficiency of energy dissipation. This suggests that H₂ formed on a pristine olivine surface should be much less rovibrationally excited than H₂ formed on a graphite surface. Gas-phase H atoms impinging on the surface will first physisorb relatively strongly  ( E _phys= 1240 K)  . The H atom can then migrate via desorption and re-adsorption, with a barrier equal to the adsorption energy. The barrier for a physisorbed H atom to become chemisorbed is equal to the physisorption energy, therefore there is almost no gas-phase barrier to chemisorption. An impinging gas-phase H atom can easily chemisorb  ( E _chem= 12 200 K)  , creating a defect where a silicate O atom is protonated and a single electron resides on the surface above the adjacent magnesium ion. This defect directs any subsequent impinging H atoms to chemisorb strongly (39 800 K) on the surface electron site. The two adjacent chemisorbed atoms can subsequently recombine to form H₂ via a barrier (5610 K) that is lower than the chemisorption energy of the second H atom. Alternatively, the adsorbed surface species can react with another incoming H atom to yield H₂ and regenerate the surface electron site. This double chemisorption 'relay mechanism' catalyzes H₂ formation on the olivine surface and is expected to attenuate the rovibrational excitation of H₂ thus formed.     

Gas-phase models for the evolved planetary nebulae NGC 6781, M4-9 and NGC 7293

We have studied the chemistry of the molecular gas in evolved planetary nebulae. Three pseudo-time-dependent gas-phase models have been constructed for dense (10⁴–10⁵ cm⁻³) and cool ( T ∼15 K) clumpy envelopes of the evolved nebulae NGC 6781, M4-9 and NGC 7293. The three nebulae are modelled as carbon-rich stars evolved from the asymptotic giant branch to the late planetary nebula phase. The clumpy neutral envelopes are subjected to ultraviolet radiation from the central star and X-rays that enhance the rate of ionization in the clumps. With the ionization rate enhanced by four orders of magnitude over that of the ISM, we find that resultant abundances of the species HCN, HNC, HC₃N and SiC₂ are in good agreement with observations, while those of CN, HCO⁺, CS and SiO are in rough agreement. The results indicate that molecular species such as CH, CH₂, CH₂⁺ , HCl, OH and H₂O are anticipated to be highly abundant in these objects.     

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.     

The 'Carina Flare' supershell: probing the atomic and molecular ISM in a Galactic chimney

The 'Carina Flare' supershell, GSH 287+04−17, is a molecular supershell originally discovered in  ¹²CO( J = 1–0)  with the NANTEN 4 m telescope. We present the first study of the shell's atomic ISM, using H  i 21-cm line data from the Parkes 64-m telescope Southern Galactic Plane Survey. The data reveal a gently expanding,  ∼230 × 360  pc H  i supershell that shows strong evidence of Galactic Plane blowout, with a break in its main body at   z ∼ 280  pc and a capped high-latitude extension reaching   z ∼ 450  pc. The molecular clouds form comoving parts of the atomic shell, and the morphology of the two phases reflects the supershell's influence on the structure of the ISM. We also report the first discovery of an ionized component of the supershell, in the form of delicate, streamer-like filaments aligned with the proposed direction of blowout. The distance estimate to the shell is re-examined, and we find strong evidence to support the original suggestion that it is located in the Carina Arm at a distance of  2.6 ± 0.4 kpc  . Associated H  i and H₂ masses are estimated as   M _H I≈ 7 ± 3 × 10⁵ M_⊙  and     , and the kinetic energy of the expanding shell as   E _K ∼ 1 × 10⁵¹  erg. We examine the results of analytical and numerical models to estimate a required formation energy of several 10⁵¹ to  ∼10⁵²  erg, and an age of  ∼10⁷ yr  . This age is compatible with molecular cloud formation time-scales, and we briefly consider the viability of a supershell-triggered origin for the molecular component.     

Molecular hydrogen in damped Lyα systems: clues to interstellar physics at high redshift

In order to interpret H₂ quasar absorption-line observations of damped Lyα systems (DLAs) and subDLAs, we model their H₂ abundance as a function of dust-to-gas ratio, including H₂ self-shielding and dust extinction against dissociating photons. Then, we constrain the physical state of the gas by using H₂ data. Using H₂ excitation data for DLAs with H₂ detections, we derive a gas density  1.5 ≲ log n (cm⁻³) ≲ 2.5  , temperature  1.5 ≲ log T (K) ≲ 3  , and an internal ultraviolet (UV) radiation field (in units of the Galactic value)  0.5 ≲ log χ≲ 1.5  . We then find that the observed relation between the molecular fraction and the dust-to-gas ratio of the sample is naturally explained by the above conditions. However, it is still possible that H₂ deficient DLAs and subDLAs with H₂ fractions less than  ∼10⁻⁶  are in a more diffuse and warmer state. The efficient photodissociation by the internal UV radiation field explains the extremely small H₂ fraction  (≲10⁻⁶)  observed for  κ≲ 1/30  (κ is the dust-to-gas ratio in units of the Galactic value); H₂ self-shielding causes a rapid increase in, and large variations of, H₂ abundance for  κ≳ 1/30  . We finally propose an independent method to estimate the star formation rates of DLAs from H₂ abundances; such rates are then critically compared with those derived from other proposed methods. The implications for the contribution of DLAs to the cosmic star formation history are briefly discussed.     

Chemical evolution ahead of Herbig–Haro objects

Compact regions of enhanced HCO⁺ and NH₃ emission have been detected close to a number of Herbig–Haro objects. An interpretation of these detections is the following: a transient clump within the molecular cloud has been irradiated by the shock that generates the Herbig–Haro object. The irradiation releases icy mantles from the grains within the transient clump and initiates a photochemistry. On the basis of this picture, we have developed an extensive chemical model which predicts that a wide range of species, other than NH₃ and HCO⁺, should also be detectable. These include CH₃OH, H₂S, C₃H₄, H₂CO, SO, SO₂, H₂CS and NS. The chemical effects should last ∼  10⁴ yr  .     

A study of the 2.5–25 μm spectrum of H2O ice

We present new absorbance spectra of the 3-, 6- and 12-μm features of amorphous and crystalline H₂O ice obtained between 10 and 140 K. Three sets of measurements have been made. In series I, the ice film was initially deposited on to a CsI substrate at 10 K and successive spectra were then obtained at intermediate temperatures as the ice was warmed up to 140 K. The second set, series II, comprises spectra for ice films deposited and measured at temperatures between 10 and 140 K. In the third set of measurements, series III, spectra were obtained for an ice film deposited at 140 K and then at intermediate temperatures as the film was cooled down to 10 K. The series I and II results show that the ice undergoes an amorphous-to-crystalline phase transition in the 110–120 K range. The 3- and 12-μm bands have similar trends in full width at half-maximum (FWHM) and opposite peak wavelength shifts. The temperature behaviour of the 6-μm band is different, as no clear phase transition temperature can be discerned from its FWHM and peak wavelength position data. In the series III spectra the peak wavelength positions and FWHM of the three bands remain relatively constant, thus demonstrating the stability of the crystalline phase against thermal cycling. A comparison between the laboratory results and astronomical spectra suggests that the identification of the librational band of H₂O ice in OH 231.8 + 4.2 may be incorrect.     

Dust and hydrogen molecules in the extremely metal-poor dwarf galaxy SBS 0335–052

During the early stages of galaxy evolution, the metallicity is generally low and nearby metal-poor star-forming galaxies may provide templates for primordial star formation. In particular, the dust content of such objects is of great importance, because early molecular formation can take place on grains. To gain insight into primeval galaxies at high redshift, we examine the dust content of the nearby extremely low-metallicity galaxy SBS  0335–052  which hosts a very young starburst (≲10⁷ yr). In young galaxies, the dust formation rate in Type II supernovae governs the amount of dust, and by incorporating recent results on dust production in Type II supernovae we model the evolution of dust content. If the star-forming region is compact (≲100 pc), as suggested by observations of SBS  0335–052  , our models consistently explain the quantity of dust, far-infrared luminosity, and dust temperature in this low-metallicity object. We also discuss the H₂ abundance. The compactness of the region is important to H₂ formation, because the optical depth of dust for UV photons becomes large and H₂ dissociation is suppressed. We finally focus on implications for damped Ly α systems.