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⁺.     

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.     

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.     

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.     

On the detection of the linear C5 molecule in the interstellar medium

An upper limit of the column density of the C₅ linear molecule in translucent interstellar clouds is estimated from high-resolution ( R =80 000) and very high signal-to-noise ratio (∼1000) echelle spectra. It is 10¹² cm⁻² per E ( B − V )=1 (two orders of magnitude lower than that of C₂).     

The contributions of J-type shocks to the H2 emission from molecular outflow sources

We present the results of modelling of the H₂ emission from molecular outflow sources, induced by shock waves propagating in the gas. We emphasize the importance of proper allowance for departures from equilibrium owing to the finite flow velocity of the hot, compressed gas, with special reference to the excitation, dissociation and reformation of H₂. The salient features of our computer code are described. The code is applied to interpreting the spectra of the outflow sources Cepheus A West and HH43. Particular attention is paid to determining the cooling times in shocks whose speeds are sufficient for collisional dissociation of H₂ to take place; the possible observational consequences of the subsequent reformation of H₂ are also examined. Because molecular outflow sources are intrinsically young objects, J-type shocks may be present in conjunction with magnetic precursors, which have a C-type structure. We note that very different physical and dynamical conditions are implied by models of C- and J-type shocks which may appear to fit the same H₂ excitation diagram.     

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.     

H2 emission from shocks in molecular outflows: the significance of departures from a stationary state

We have computed the time dependence of the H₂ rovibrational emission spectrum from molecular outflows. This emission arises in shock waves generated by the impact of jets, associated with low-mass star formation, on molecular gas. The shocks are unlikely to have attained a state of equilibrium, and so their structure will exhibit both C- and J-type characteristics. The rotational excitation diagram is found to provide a measure of the age of the shock; in the case of the outflow observed in Cepheus A West by the ISO satellite, the shock age is found to be approximately 1.5×10³ yr. Emission by other species, such as NH₃ and SiO, is also considered, as are the intensities of the fine-structure transitions of atoms and ions.     

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.