Interstellar Formation of Thioethanal (CH$_{3}$CHS). Gas-Phase and Ice-Surface Mechanisms involving Secondary Sulfur Products

TL;DR

This study investigates the formation mechanisms of sulfur-bearing molecule thioethanal (CH3CHS) in interstellar environments, revealing barrierless formation pathways and the influence of ice-surface chemistry, with implications for astrochemical observations.

Contribution

It introduces a detailed computational analysis of thioethanal formation pathways in gas and ice phases, including the first accurate binding energy on water ice, advancing understanding of sulfur chemistry in space.

Findings

Barrierless formation of CH3CHS in gas phase.

Surface environments modulate activation barriers.

Sulfur chemistry enables alternative pathways, affecting yields.

Abstract

The formation pathways of sulfur-bearing species in the interstellar medium are crucial to understand astrochemical processes in cold molecular clouds and to gain new insights about the sulfur budget in these regions. We aim to explore the recently detected, thioethanal (CH$_{3}$CHS) formation mechanisms from thioethanol (CH$_{3}$CH$_{2}$SH) as a precursor in addition to secondary sulfur products. The electronic structure methods and density functional theory for both gas-phase and ice-grain surface environments is employed. To mimic interstellar ice-mantles, we use medium (W6) and large amorphized (W22) water clusters as implemented in Binding Energy Evaluation protocol. A barrierless formation mechanism for CH$_{3}$CHS under low-temperature interstellar conditions is identified, in the gas phase. Surface environments modulate activation barriers in a site-specific manner, elucidated through both Langmuir-Hinshelwood and Eley-Rideal initiated surface reaction pathways. Compared to oxygen analogs, sulfur chemistry enables alternate pathways due to weaker S-H bonding, with a competing route forming ethane-1,1-di-thiol (CH$_{3}$CH(SH)SH), on the ice-grain surface, potentially reducing CH$_{3}$CHS yields. The first accurate binding energy for thioethanol on water ice is also reported, confirming its greater volatility than ethanol. The proposed mechanism offers a tentative hypothesis for the apparent mutual exclusive detections of the CH$_{3}$CH$_{2}$SH and CH$_{3}$CHS in TMC-1, Orion, and Sgr B2(N), that further requires validation through quantitative astrochemical modeling and also to distinguish this chemical differentiation from observational sensitivity limitations. These qualitative findings highlight the multifaceted chemical behavior of sulfur-bearing organics in the interstellar medium and support CH$_{3}$CH(SH)SH as promising astro-chemical targets.