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.     

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.     

Molecular hydrogen formation on porous dust grains

Recent laboratory experiments on interstellar dust analogues have shown that H₂ formation on dust-grain surfaces is efficient in a range of grain temperatures below 20 K. These results indicate that surface processes may account for the observed H₂ abundance in cold diffuse and dense clouds. However, high abundances of H₂ have also been observed in warmer clouds, including photon-dominated regions (PDRs), where grain temperatures may reach 50 K, making the surface processes extremely inefficient. It was suggested that this apparent discrepancy can be resolved by chemisorption sites. However, recent experiments indicate that chemisorption processes may not be efficient at PDR temperatures. Here we consider the effect of grain porosity on H₂ formation, and analyse it using a rate-equation model. It is found that porosity extends the efficiency of the recombination process to higher temperatures. This is because H atoms that desorb from the internal surfaces of the pores may re-adsorb many times and thus stay longer on the surface. However, this porosity-driven extension may enable efficient H₂ formation in PDRs only if porosity also contributes to significant cooling of the grains, compared to non-porous grains.     

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.     

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.     

The excitation and kinematical properties of H2 and [Fe ii] in the HH 46/47 bipolar outflow

Long-slit spectra of the molecular outflow Herbig–Haro (HH) 46/47 have been taken in the J and K near-infrared bands. The observed H₂ line emission confirms the existence of a bright and extended redshifted counter-jet outflow south-west of HH 46. In contrast with the optical appearance of this object, we show that this outflow seems to be composed of two different emission regions characterized by distinct heliocentric velocities. This implies an acceleration of the counter-jet.
The observed [Fe  ii ] emission suggests an average extinction of 7–9 visual magnitudes for the region associated with the counter-jet.
Through position–velocity diagrams, we show the existence of different morphologies for the H₂ and [Fe  ii ] emission regions in the northern part of the HH 46/47 outflow. We have detected for the first time high-velocity (−250 km s⁻¹) [Fe  ii ] emission in the region bridging HH 46 to HH 47A. The two strong peaks detected can be identified with the optical positions B8 and HH 47B.
The H₂ excitation diagrams for the counter-jet shock suggest an excitation temperature for the gas of T _ex≈2600 K . The lack of emission from the higher energy H₂ lines, such as the 4–3 S(3) transition, suggests a thermal excitation scenario for the origin of the observed emission. Comparison of the H₂ line ratios with various shock models yielded useful constraints about the geometry and type of these shocks. Planar shocks can be ruled out whereas curved or bow shocks (both J- and C-type) can be parametrized to fit our data.     

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.     

Molecular hydrogen emission in Cygnus A

We present J , H and K -band spectroscopy of Cygnus A, spanning 1.0–2.4 μm in the rest-frame and hence several rovibrational H₂, H recombination and [Fe  ii ] emission lines. The lines are spatially extended by up to 6 kpc from the nucleus, but their distinct kinematics indicate that the three groups (H, H₂ and [Fe  ii ]) are not wholly produced in the same gas. The broadest line, [Fe  ii ] λ 1.644, exhibits a non-Gaussian profile with a broad base (FWHM≃1040 km s⁻¹), perhaps because of the interaction with the radio source. Extinctions to the line-emitting regions substantially exceed earlier measurements based on optical H recombination lines.
Hard X-rays from the quasar nucleus are likely to dominate the excitation of the H₂ emission. The results of Maloney, Hollenbach & Tielens are thus used to infer the total mass of gas in H₂ v=1–0 S(1)-emitting clouds as a function of radius, for gas densities of 10³ and 10⁵ cm⁻³, and stopping column densities N _H=10²²–10²⁴ cm⁻². Assuming azimuthal symmetry, at least 2.3×10⁸ M_⊙ of such material is present within 5 kpc of the nucleus, if the line-emitting clouds see an unobscured quasar spectrum. Alternatively, if the bulk of the X-ray absorption to the nucleus inferred by Ueno et al. actually arises in a circumnuclear torus, the implied gas mass rises to ∼10¹⁰ M_⊙. The latter plausibly accounts for 10⁹ yr of mass deposition from the cluster cooling flow, for which within this radius.     

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.     

On the possibility of observing H2 emission from primordial molecular cloud kernels

We study the prospects for observing H₂ emission during the assembly of primordial molecular cloud kernels. The primordial molecular cloud cores, which resemble those at the present epoch, can emerge around  1+ z ∼20  according to recent numerical simulations. The kernels form inside the cores, and the first stars will appear inside the kernels. A kernel typically contracts to form one of the first generation stars with an accretion rate that is as large as ∼0.01 M_⊙ yr⁻¹. This occurs owing to the primordial abundances, which result in a kernel temperature of order 1000 K, and the collapsing kernel emits H₂ line radiation at a rate ∼10³⁵ erg s⁻¹. Predominantly   J =5-3   ( v =0)  rotational emission of H₂ is expected. At redshift  1+ z ∼20  , the expected flux is ∼0.01 μJy for a single kernel. While an individual object is not observable by any facilities available in the near future, the expected assembly of primordial star clusters on subgalactic scales can result in fluxes at the sub-mJy level. This is marginally observable with ASTRO-F and ALMA. We also examine the rotational   J =2-0   ( v =0)  and vibrational   δv =1  emission lines. The former may possibly be detectable with ALMA.     

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.     

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.     

Gas-phase mean opacities for varying [M/H], N/O and C/O

We present a set of gas-phase Planck mean and Rosseland mean opacity tables applicable for simulations of star and planet formation, stellar evolution and disc modelling at various metallicities in hydrogen-rich environments. The tables are calculated for gas temperatures between 1000 and 10 000 K and total hydrogen number densities between 10² and  10¹⁷ cm⁻³  . The carbon-to-oxygen ratio is varied from 0.43 to well above 2.0, the nitrogen-to-oxygen ratio between 0.14 and 100.0. The tables are calculated for a range of metallicities down to  [M/H]'= log  N _M/ N _H=−7.0  . We demonstrate how the mean opacities and the abundances of the opacity species vary with C/O, N/O and  [M/H]'  . We use the element abundances from Grevesse et al., and we provide additional tables for the oxygen abundance value from Caffau et al. All tables will be available online at http://star-www.st-and.ac.uk/~ch80/datasources.html .     

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.     

ISO observations of molecular hydrogen in the DR 21 bipolar outflow

We demonstrate that a wide range of molecular hydrogen excitation can be observed in protostellar outflows at wavelengths in excess of 5 μm. Cold H₂ in DR 21 is detected through the pure rotational transitions in the ground vibrational level (0–0). Hot H₂ is detected in pure rotational transitions within higher vibrational levels (1–1, 1–2, etc.). Although this emission is relatively weak, we have detected two 1–1 lines in the DR 21 outflow with the ISO SWS instrument. We thus investigate molecular excitation over energy levels corresponding to the temperature range 1015–15 722 K, without the uncertainty introduced by differential extinction when employing near-infrared data.
This gas is thermally excited. We uncover a rather low H₂ excitation in the DR 21 West Peak. The line emission cannot be produced from single C-shocks or J-shocks; a range of shock strengths is required. This suggests that bow shocks and/or bow-generated supersonic turbulence is responsible. We are able to distinguish this shock-excited gas from the fluoresced gas detected in the K band, providing support for the dual-excitation model of Fernandes, Brand & Burton.     

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.     

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.     

Shocked molecular gas towards the supernova remnant G359.1–0.5 and the Snake

We have found a bar of shocked molecular hydrogen (H₂) towards the OH(1720 MHz) maser located at the projected intersection of supernova remnant (SNR)  G359.1–0.5  and the non-thermal radio filament known as the Snake. The H₂ bar is well aligned with the SNR shell and almost perpendicular to the Snake. The OH(1720 MHz) maser is located inside the sharp western edge of the H₂ emission, which is consistent with the scenario in which the SNR drives a shock into a molecular cloud at that location. The spectral line profiles of ¹²CO, HCO⁺ and CS towards the maser show broad-line absorption, which is absent in the ¹³CO spectra and most probably originates from the pre-shock gas. A density gradient is present across the region and is consistent with the passage of the SNR shock, while the H₂ filament is located at the boundary between the pre-shock and post-shock regions.     

The rotational excitation of H2 by H2

We present rate coefficients for rotational transitions induced in collisions between H₂ molecules. Rotational levels J  ≤ 8 and kinetic temperatures T  ≤ 1000 K are considered. The interaction potential computed by Schwenke has been used, together with the quantal coupled channels method of calculating the cross-sections. Comparison is made with the more recent of previous results.     

A shallow though extensive H2 2.122-μm imaging survey of Taurus–Auriga–Perseus – I. NGC 1333, L1455, L1448 and B1

We discuss wide-field near-infrared (near-IR) imaging of the NGC 1333, L1448, L1455 and B1 star-forming regions in Perseus. The observations have been extracted from a much larger narrow-band imaging survey of the Taurus–Auriga–Perseus complex. These H₂ 2.122-μm observations are complemented by broad-band K imaging, mid-IR imaging and photometry from the Spitzer Space Telescope , and published submillimetre CO   J = 3–2  maps of high-velocity molecular outflows. We detect and label 85 H₂ features and associate these with 26 molecular outflows. Three are parsec-scale flows, with a mean flow lobe length exceeding 11.5 arcmin. 37 (44 per cent) of the detected H₂ features are associated with a known Herbig–Haro object, while 72 (46 per cent) of catalogued HH objects are detected in H₂ emission. Embedded Spitzer sources are identified for all but two of the 26 molecular outflows. These candidate outflow sources all have high near-to-mid-IR spectral indices (mean value of  α∼ 1.4  ) as well as red IRAC 3.6–4.5 μm and IRAC/MIPS 4.5–24.0 μm colours: 80 per cent have [3.6]–[4.5] > 1.0 and [4.5]–[24] > 1.5. These criteria – high α and red [4.5]–[24] and [3.6]–[4.5] colours – are powerful discriminants when searching for molecular outflow sources. However, we find no correlation between α and flow length or opening angle, and the outflows appear randomly orientated in each region. The more massive clouds are associated with a greater number of outflows, which suggests that the star formation efficiency is roughly the same in each region.