Formation of Formic Acid, Formaldehyde, and Carbon Dioxide by Electron-Induced Chemistry in Ices of Water and Carbon Monoxide

The processing of cryogenic ices consisting of water and carbon monoxide by different types of radiation is known to lead to the formation of carbon dioxide, formic acid, formaldehyde, and also methanol. In this study, we have investigated these reactions upon electron irradiation with energies between 2 and 20 eV, an energy range typically found in secondary electrons. This is the first time that the reactions have been monitored with a sufficiently fine step width in energy to resolve and identify the primary electron–molecule interactions leading to the specific products. This enables us to elucidate reaction mechanisms by linking these primary electron–molecule interactions to final products. In these reactions, HCO• and HOCO• radicals are key intermediates. Our results show that the HCO• intermediate predominantly leads to formaldehyde, while HOCO• is intermediate to the formation of formic acid. Noticeably, the formation of both formaldehyde and formic acid is enhanced within characteristic energy ranges by resonant electron attachment processes. In contrast, the reactions leading to carbon dioxide show no resonant energy dependence but can be traced back to nonresonant neutral dissociation processes. This reveals that carbon dioxide is linked to neither of these two intermediates. This is in contrast to prior experimental studies, which have proposed that carbon dioxide is formed by loss of a H• radical from HOCO•. However, our results confirm theoretical studies that have predicted that carbon dioxide formation from HOCO• is not very efficient, because HOCO• presents an energetic well and quickly loses any excess energy it might have in an ice matrix. Instead, we provide evidence that the primary electron–molecule interaction leading to the formation of carbon dioxide in cryogenic ices of water and carbon monoxide is the neutral dissociation of water into O atoms and H2. The so-formed O atoms then react directly with carbon monoxide to yield carbon dioxide.