Interstellar hide and go seek: C3H4O. There and back (again)

The molecular species C3H4O represents a striking example of an astrochemical conundrum. With more than 60 structural isomers theoretically possible, to date only acrolein (CH2CHCHO) has been identified in the Sgr B2(N) region of the interstellar medium (ISM). The topography of the singlet potential...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2022-08, Vol.24 (32), p.19184-19198
Main Authors: Field-Theodore, Terri E, Taylor, Peter R
Format: Article
Language:English
Subjects:
Astrochemistry
Interstellar chemistry
Interstellar matter
Interstellar space
Isomers
Mathematical analysis
Potential energy
Propargyl alcohol
Reaction mechanisms
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Summary:The molecular species C3H4O represents a striking example of an astrochemical conundrum. With more than 60 structural isomers theoretically possible, to date only acrolein (CH2CHCHO) has been identified in the Sgr B2(N) region of the interstellar medium (ISM). The topography of the singlet potential energy surface is complicated, with three low-lying minima predicted to be almost isoenergetic: cis and trans-acrolein, and methylketene (CH3CHCO). Our CCSD(T)/cc-pVTZ calculations confirm that methylketene is energetically lower than cis-acrolein, lying only 1.9 kJ mol−1 above the trans-isomer, which is the global minimum. In this respect, methylketene is a promising candidate for interstellar observation. Unfortunately, however, despite several searches its astronomical detection has been unsuccessful. To this end, the key question is whether in fact methylketene exists as a discrete chemical entity in the ISM at all? In this paper, we present a detailed examination of the C3H4O potential energy surface, with specific focus on formation pathways. CCSD(T)/cc-pVTZ calculations enable a more elaborate interpretation of reaction mechanisms than was published hitherto. Our results show that gauche-propargyl alcohol and syn and anti-allenol emerge as interesting new targets for observational astronomers in TMC-1: given the recent discovery of the propargyl radical in this region, barrierless product channels involving OH· lend support to their candidacy as possible interstellar species. Finally, this work provides accurate spectral data of these three potential molecules, to be used for searches in interstellar space.
ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp00995a