ON THE FORMATION OF CO2 AND OTHER INTERSTELLAR ICES

We investigate the formation and evolution of interstellar dust-grain ices under dark-cloud conditions, with a particular emphasis on CO2. 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 CO2, 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 CO2 ice production in dark clouds. At low visual extinctions, with dust temperatures >= 12 K, CO2 is formed by direct diffusion and reaction of CO with OH; we associate the resultant CO2-rich ice with the observational polar CO2 signature. CH4 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:CO2 ratio in the range similar to 2-4, which we associate with apolar signatures. We suggest that the observational apolar CO2/CO ice signatures in dark clouds result from a strongly segregated CO:H2O ice, in which CO2 resides almost exclusively within the CO component. Observed visual-extinction thresholds for CO2, CO, and H2O are well reproduced by depth-dependent models. Methanol formation is found to be strongly sensitive to dynamical timescales and dust temperatures.