On the Formation of Co₂and Other Interstellar Ices

We investigate the formation and evolution of interstellar dust-grain ices under dark-cloud conditions, with a particular emphasis on CO 2 . We use a three-phase model (gas/surface/mantle) to simulate the coupled gas–grain chemistry, allowing the distinction of the chemically active surface from the ice layers preserved in the mantle beneath. The model includes a treatment of the competition between barrier-mediated surface reactions and thermal-hopping processes. The results show excellent agreement with the observed behavior of CO 2 , CO, and water ice in the interstellar medium. The reaction of the OH radical with CO is found to be efficient enough to account for CO 2 ice production in dark clouds. At low visual extinctions, with dust temperatures ≳12 K, CO 2 is formed by direct diffusion and reaction of CO with OH; we associate the resultant CO 2 -rich ice with the observational polar CO 2 signature. CH 4 ice is well correlated with this component. At higher extinctions, with lower dust temperatures, CO is relatively immobile and thus abundant; however, the reaction of H and O atop a CO molecule allows OH and CO to meet rapidly enough to produce a CO:CO 2 ratio in the range ∼2–4, which we associate with apolar signatures. We suggest that the observational apolar CO 2 /CO ice signatures in dark clouds result from a strongly segregated CO:H 2 O ice, in which CO 2 resides almost exclusively within the CO component. Observed visual-extinction thresholds for CO 2 , CO, and H 2 O are well reproduced by depth-dependent models. Methanol formation is found to be strongly sensitive to dynamical timescales and dust temperatures.