Mechanisms of methyl formate production during electron-induced processing of methanol-carbon monoxide ices.

The formation of methyl formate (CH3OCHO) upon electron irradiation of mixed ices of carbon monoxide (CO) and methanol (CH3OH) has been monitored by post-irradiation thermal desorption spectrometry (TDS). The energy dependence of the product yields obtained with electron energies between 3 and 18 eV was studied. These energies are characteristic of secondary electrons that are released in vast numbers under the effect of ionizing radiation. Our results reveal that the reactions leading to methyl formate are initiated by a number of different electron-molecule interactions that produce CH3O˙ radicals. Dissociative electron attachment (DEA) to CH3OH around 5.5 eV and neutral dissociation (ND) above 7 eV release CH3O˙ radicals that can add to CO to initiate a reaction sequence leading to formation of methyl formate. Around 10 eV, DEA to CO yields an oxygen radical anion that reacts with CH3OH to also produce CH3O˙ radicals. Alternatively, CH3OH can also release H˙ radicals upon both DEA and ND. These can also add to CO to form HCO˙ radicals as an intermediate to formaldehyde (H2CO), which was also investigated to unravel the reaction mechanisms leading to formation of methyl formate. The recombination of HCO˙ and CH3O˙ as minority radical species is considered as an alternative but less probable pathway to the formation of methyl formate. To the best of our knowledge, this is the first study showing considerable contributions of DEA to the formation of methyl formate in CH3OH containing ices. Thus, our study has important implications for current astrochemical models.

Electron-Induced Formation of Ethyl Methyl Ether in Condensed Mixtures of Methanol and Ethylene.

Electron-induced reactions in condensed mixtures of ethylene (C2H4) and methanol (CH3OH) lead to the formation of ethyl methyl ether (EME, C2H5OCH3), as shown by post-irradiation thermal desorption spectrometry (TDS). In contrast to the electron-induced reaction between water (H2O) and C2H4, product formation as a consequence of proton transfer following electron attachment (EA) to C2H4 is not observed in the analogous reaction between CH3OH and C2H4. However, a resonant process centered around 5.5 eV and a threshold-type increase of product yield starting at 9 eV is observed. On the basis of the presence and absence of particular side products after irradiation of the mixture as well as of the pure parent compounds, reaction mechanisms related to the two energy regimes are proposed. Below the ionization threshold of the reactants, dissociative electron attachment (DEA) to CH3OH triggers the reaction sequence by producing reactive methoxy radicals, which attack neighboring C2H4 molecules. The resulting adduct then abstracts a hydrogen atom to yield EME. Above but near the ionization threshold, electron impact ionization (EI) produces primarily intact molecular cations, which drive the reaction by converting the repulsive Coulomb force between the high electron densities at the reactive sites of the two neutral parent species into an attractive force. This again induces the formation of an adduct between the two reactants that rearranges to the product EME. Fragmentation of the molecular CH3OH+• cation into CH3O+, however, may provide an additional reaction pathway toward EME. In this scenario, CH3O+ attacks a neighboring C2H4 molecule. The resulting adduct is then neutralized by a thermalized electron and abstracts a hydrogen atom from a nearby CH3OH molecule to yield EME.