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.     

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.     

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 ortho- to para- ratio of H2 in the starburst of NGC 253

We present measurements of several near-infrared emission lines from the nearby galaxy NGC 253. We have been able to measure four H₂ lines across the circumnuclear starburst, from which we estimate the ortho- to para- ratio of excited H₂ to be ∼2. This indicates that the bulk of the H₂ emission arises from photodissociation regions (PDRs), rather than from shocks. This is the case across the entire region of active star formation.
As the H₂ emission arises from PDRs, it is likely that the ratio of H₂ to Brγ (the bright hydrogen recombination line) is a measure of the relative geometry of O and B stars and PDRs. Towards the nucleus of NGC 253 the geometry is deduced to be tightly clustered O and B stars in a few giant H  II regions that are encompassed by PDRs. Away from the nuclear region, the geometry becomes that of PDRs bathed in a relatively diffuse ultraviolet radiation field.
The rotation curves of 1–0 S(1) and Brγ suggest that the ionized gas is tracing a kinetic system different from that of the molecular gas in NGC 253, particularly away from the nucleus.     

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.     

Unlocking the Keyhole: H2 and PAH emission from molecular clumps in the Keyhole Nebula

To better understand the environment surrounding CO emission clumps in the Keyhole Nebula, we have made images of the region in H₂ 1–0 S(1) (2.122-μm) emission and polycyclic aromatic hydrocarbon (PAH) emission at 3.29 μm. Our results show that the H₂ and PAH emission regions are morphologically similar, existing as several clumps, all of which correspond to CO emission clumps and dark optical features. The emission confirms the existence of photodissociation regions (PDRs) on the surface of the clumps. By comparing the velocity range of the CO emission with the optical appearance of the H₂ and PAH emission, we present a model of the Keyhole Nebula whereby the most negative velocity clumps are in front of the ionization region, the clumps at intermediate velocities are in it and those which have the least negative velocities are at the far side. It may be that these clumps, which appear to have been swept up from molecular gas by the stellar winds from η  Car, are now being overrun by the ionization region and forming PDRs on their surfaces. These clumps comprise the last remnants of the ambient molecular cloud around η Car.     

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.     

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.     

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.     

Formation of CO2 on a carbonaceous surface: a quantum chemical study

The formation of CO₂ in the gas phase and on a polyaromatic hydrocarbon surface (coronene) via three possible pathways is investigated with density functional theory. Calculations show that the coronene surface catalyses the formation of CO₂ on model grain surfaces. The addition of ³O to CO is activated by 2530 K in the gas phase. This barrier is lowered by 253 K for the Eley–Rideal mechanism and 952 K for the hot-atom mechanism on the surface of coronene. Alternative pathways for the formation of CO₂ are the addition of ³O to the HCO radical, followed by dissociation of the HCO₂ intermediate. The O + HCO addition is barrierless in the gas phase and on the surface and is more than sufficiently exothermic to subsequently cleave the H–C bond. The third mechanism, OH + CO addition followed by H removal from the energized HOCO intermediate, has a gas-phase exit barrier that is 1160 K lower than the entrance barrier. On the coronene surface, however, both barriers are almost equal. Because the HOCO intermediate can also be stabilized by energy dissipation to the surface, it is anticipated that for the surface reaction the adsorbed HOCO could be a long-lived intermediate. In this case, the stabilized HOCO intermediate could react, in a barrierless manner, with a hydrogen atom to form H₂+ CO₂, HCO₂H, or H₂O + CO.     

Universal gas density and temperature profile

We explore possibilities of collapse and star formation in Population III objects exposed to the external ultraviolet background (UVB) radiation. Assuming spherical symmetry, we solve self-consistently radiative transfer of photons, non-equilibrium H₂ chemistry and gas hydrodynamics. Although the UVB does suppress the formation of low-mass objects, the negative feedback turns out to be weaker than previously suggested. In particular, the cut-off scale of collapse drops significantly below the virial temperature T _vir∼10⁴ K at weak UV intensities ( J ₂₁≲10⁻²) , owing to both self-shielding of the gas and H₂ cooling. Clouds above this cut-off tend to contract highly dynamically, further promoting self-shielding and H₂ formation. For plausible radiation intensities and spectra, the collapsing gas can cool efficiently to temperatures well below 10⁴ K before rotationally supported and the final H₂ fraction reaches ∼ 10⁻³.
Our results imply that star formation can take place in low-mass objects collapsing in the UVB. The threshold baryon mass for star formation is ∼ 10⁹ M_⊙ for clouds collapsing at redshifts z ≲3 , but drops significantly at higher redshifts. In a conventional cold dark matter universe, the latter coincides roughly with that of the 1 σ density fluctuations. Objects near and above this threshold can thus constitute 'building blocks' of luminous structures, and we discuss their links to dwarf spheroidal/elliptical galaxies and faint blue objects. These results suggest that the UVB can play a key role in regulating the star formation history of the Universe.     

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.     

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.     

Thermal desorption of water ice in the interstellar medium

Water (H₂O) ice is an important solid constituent of many astrophysical environments. To comprehend the role of such ices in the chemistry and evolution of dense molecular clouds and comets, it is necessary to understand the freeze-out, potential surface reactivity and desorption mechanisms of such molecular systems. Consequently, there is a real need from within the astronomical modelling community for accurate empirical molecular data pertaining to these processes. Here we give the first results of a laboratory programme to provide such data. Measurements of the thermal desorption of H₂O ice, under interstellar conditions, are presented. For ice deposited under conditions that realistically mimic those in a dense molecular cloud, the thermal desorption of thin films (≪50 molecular layers) is found to occur with zeroth-order kinetics characterized by a surface binding energy, E _des, of 5773 ± 60 K, and a pre-exponential factor, A , of 10^30 ± 2 molecules cm⁻² s⁻¹. These results imply that, in the dense interstellar medium, thermal desorption of H₂O ice will occur at significantly higher temperatures than has previously been assumed.     

Shocked gas around Cepheus A: evidence for multiple outflows from H2S and SO2 observations

The Cepheus A star-forming region has been investigated through a multiline H₂S and SO₂ survey at millimetre wavelengths. Large-scale maps and high-resolution line profiles reveal the occurrence of several outflows. Cep A East is associated with multiple mass-loss processes: in particular, we detect a 0.6-pc jet-like structure which shows for the first time that the Cep A East young stellar objects are driving a collimated outflow moving towards the south.
The observed outflows show different clumps associated with definitely different H₂S/SO₂ integrated emission ratios, indicating that the gas chemistry in Cepheus A has been altered by the passage of shocks. H₂S appears to be more abundant than SO₂ in high-velocity clumps, in agreement with chemical models. However, we also find quite small H₂S linewidths, suggestive of regions where the evaporated H₂S molecules had enough time to slow down but not to freeze out on to dust grains. Finally, comparison between the line profiles indicates that the excitation conditions increase with the velocity, as expected for a propagation of collimated bow shocks.     

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.     

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.     

The integrated bispectrum as a test of cosmic microwave background non-Gaussianity: detection power and limits on fNL with WMAP data

We note that H₂ emitting planetary nebulae tend to have Zanstra temperatures   T _Z(He  ii ) > 90 kK  . This is shown to be consistent with a large evolutionary lifetime, and the kinematic ages of the envelopes. Non-local thermodynamic equilibrium stellar atmospheric modelling also shows that levels of soft X-ray emission increase more rapidly than has previously been assumed, and are preferentially large in H₂ emitting sources. It is suggested that this may hold the key to explaining the strengths of the H₂ transitions.     

Further 2MASS mapping of hot dust in planetary nebulae

We have used 2 Micron All Sky Survey (2MASS) mapping results to investigate the distribution of hot dust continua in 12 planetary nebulae (PNe). The nature of this emission is unclear, but it is possible that where the continuum is extended, as is the case for M 1-12 and NGC 40, then the grains concerned may be very small indeed. The absorption of individual photons by such grains may lead to sharp spikes in temperature, as has previously discussed for several other such outflows. Other sources (such as MaC 1-4, He 2-25, B1 2-1 and K 3-15) appear to be relatively compact, and the high temperatures observed are understandable in terms of more normal heating processes. It is possible that the grains in these cases are experiencing high radiant flux levels.
Finally, it is noted that whilst the core of M 2-2 appears to show hot grain emission, this is less the case for its more extended envelope. The situation may, in this case, be similar to that of NGC 2346, in which much of the emission is located within an unresolved nucleus. Similarly, it is noted that in addition to hot dust and gas thermal continua, the emission in the interior of NGC 40 may be enhanced through rotational–vibrational transitions of H₂, and/or the 2p³P⁰–2s³S transition of He  i .     

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.