Binding energies of ethanol and ethylamine on interstellar water ices: synergy between theory and experiments.

Experimental and computational chemistry are two disciplines used to conduct research in astrochemistry, providing essential reference data for both astronomical observations and modeling. These approaches not only mutually support each other, but also serve as complementary tools to overcome their respective limitations. Leveraging on such synergy, we characterized the binding energies (BEs) of ethanol (CH3CH2OH) and ethylamine (CH3CH2NH2), two interstellar complex organic molecules (iCOMs), on crystalline and amorphous water ices through density functional theory (DFT) calculations and temperature-programmed desorption (TPD) experiments. Experimentally, CH3CH2OH and CH3CH2NH2 behave similarly, in which desorption temperatures are higher on the water ices than on a bare gold surface. Computed cohesive energies of pure ethanol and ethylamine bulk structures allow describing of the BEs of the pure species deposited on the gold surface, as extracted from the TPD curve analyses. The BEs of submonolayer coverages of CH3CH2OH and CH3CH2NH2 on the water ices cannot be directly extracted from TPD due to their co-desorption with water, but they are computed through DFT calculations, and found to be greater than the cohesive energy of water. The behaviour of CH3CH2OH and CH3CH2NH2 is different when depositing adsorbate multilayers on the amorphous ice, in that, according to their computed cohesive energies, ethylamine layers present weaker interactions compared to ethanol and water. Finally, from the computed BEs of ethanol, ethylamine and water, we can infer that the snow-lines of these three species in protoplanetary disks will be situated at different distances from the central star. It appears that a fraction of ethanol and ethylamine is already frozen on the grains in the water snow-lines, causing their incorporation in water-rich planetesimals.

Non-energetic Formation of Ethanol via CCH Reaction with Interstellar H2O Ices. A Computational Chemistry Study.

Ethanol (CH3CH2OH) is a relatively common molecule, often found in star-forming regions. Recent studies suggest that it could be a parent molecule of several so-called interstellar complex organic molecules (iCOMs). However, the formation route of this species remains under debate. In the present work, we study the formation of ethanol through the reaction of CCH with one H2O molecule belonging to the ice as a test case to investigate the viability of chemical reactions based on a "radical + ice component" scheme as an alternative mechanism for the synthesis of iCOMs, beyond the usual radical-radical coupling. This has been done by means of DFT calculations adopting two clusters of 18 and 33 water molecules as ice models. Results indicate that CH3CH2OH can potentially be formed by this proposed reaction mechanism. The reaction of CCH with H2O on the water ice clusters can be barrierless (because of the help of boundary icy water molecules acting as proton-transfer assistants), leading to the formation of vinyl alcohol precursors (H2CCOH and CHCHOH). Subsequent hydrogenation of vinyl alcohol yielding ethanol is the only step presenting a low activation energy barrier. We finally discuss the astrophysical implications of these findings.