Modeling Gas‐Grain Chemistry with Quantum Chemical Cluster Calculations. I. Heterogeneous Hydrogenation of CO and H2CO on Icy Grain Mantles

Formaldehyde (H 2 CO) and methanol (CH 3 OH) are thought to be produced in the interstellar medium by the successive hydrogenation of carbon monoxide (CO) on grain surfaces. In the gas phase, the steps in which H adds to CO and H 2 CO possess modest barriers and are too inefficient to account for the observed abundances. Recent laboratory work has confirmed that formaldehyde and methanol are formed when H atoms are deposited on CO ice at 12 K. The present study employs ab initio quantum chemical calculations to investigate the impact of water ice on the sequential hydrogenation of CO. The most favorable pathway is CO → HCO (formyl radical) → H 2 CO → CH 3 O (methoxy radical) → CH 3 OH. There is sufficient reaction energy in the final step to fragment CH 3 OH into methyl and hydroxyl radicals, which can be hydrogenated to yield methane and water, as observed in the experimental work. The emphasis here was on the two steps with barriers, H + CO and H + H 2 CO, with both addition and abstraction considered for the latter. Calculations with up to four explicit water molecules were performed, as well as further modeling to incorporate bulk effects. While ice was found to have a nearly negligible impact on H + CO → HCO, it modestly enhances the addition reaction H + H 2 CO → CH 3 O and hinders the abstraction reaction H + H 2 CO → H 2 + HCO. The deuterium-substituted reactions D + CO → DCO and D + H 2 CO → CDH 2 O were found to be slightly favored over the corresponding H reactions, particularly in the latter case. Overall, the energetics are not favorable: water ice is evidently not a good catalytic substrate for H + CO or H + H 2 CO addition reactions at very cold temperatures.