Quantum mechanical modeling of the grain-surface formation of acetaldehyde on H$_2$O:CO dirty ice surfaces

TL;DR

This study uses quantum mechanical modeling to investigate a proposed grain-surface pathway for acetaldehyde formation on icy interstellar grains, finding that the reaction likely faces significant energy barriers, making it an unlikely formation route in space.

Contribution

The paper introduces a detailed ab initio analysis of a new grain-surface formation pathway for acetaldehyde, challenging its viability in the interstellar medium.

Findings

Reaction barriers are high, hindering formation in the ISM.

Hydrogenation step is barrierless with correct orientation.

Proposed pathway is unlikely to occur in space.

Abstract

Acetaldehyde (CH$_3$CHO) is one of the most detected interstellar Complex Organic Molecule (iCOM) in the interstellar medium (ISM). These species have a potential biological relevance, as they can be precursors of more complex species from which life could have emerged. The formation of iCOMs in the ISM is a challenge and a matter of debate, whether gas-phase, grain-surface chemistry or both are needed for their synthesis. In the gas-phase, CH$_3$CHO can be efficiently synthesized from ethanol and/or ethyl radical. On the grain-surfaces, radical-radical recombinations were traditionally invoked. However, several pitfalls have been recently identified, such as the presence of energy barriers and competitive side reactions (i.e., H abstractions). Here we investigate a new grain-surface reaction pathway for the formation of acetaldehyde, namely the reaction between CH$_3$ and a CO molecule of a dirty water/CO ice followed by hydrogenation of its product, CH$_3$CO. To this end, we carried out \textit{ab initio} computations of the reaction occurring on an ice composed by 75% water and 25% CO molecules. We found that the CH$_3$ + CO$_{(ice)}$ reaction exhibits barriers difficult to overcome in the ISM, either adopting a Langmuir-Hinshelwood or an Eley-Rideal mechanism. The subsequent hydrogenation step is found to be barrierless, provided that the two reacting species have the correct orientation. Therefore, this pathway seems unlikely to occur in the ISM.