The formation of complex organic molecules by simulated secondary electrons generated in the track of galactic cosmic rays was investigated in interstellar ice analogs composed of methanol and carbon dioxide. The processed ices were subjected to temperature-programmed desorption to mimic the transition of a cold molecular cloud to a warmer star-forming region. Reaction products were detected as they sublime using photoionization reflectron time-of-flight mass spectrometry. By employing isotopic labeling, tunable photoionization and computed adiabatic ionization energies isomers of C2H4O3were investigated. Product molecules carbonic acid monomethyl ester (CH3OCOOH) and glycolic acid (HOCH2COOH) were identified. The abundance of the reactants detected in analog interstellar ices and the low irradiation dose necessary to form these products indicates that these molecules are exemplary candidates for interstellar detection. Molecules sharing a tautomeric relationship with glycolic acid, dihydroxyacetaldehyde ((OH)2CCHO), and the enol ethenetriol (HOCHC(OH)2), were not found to form despite ices being subjected to conditions that have successfully produced tautomerization in other ice analog systems.
Carbonyl-bearing complex organic molecules (COMs) in the interstellar medium (ISM) are of significant importance due to their role as potential precursors to biomolecules. Simple aldehydes and ketones like acetaldehyde, acetone, and propanal have been recognized as fundamental molecular building blocks and tracers of chemical processes involved in the formation of distinct COMs in molecular clouds and star-forming regions. Although previous laboratory simulation experiments and modeling established the potential formation pathways of interstellar acetaldehyde and propanal, the underlying formation routes to the simplest ketone—acetone—in the ISM are still elusive. Herein, we performed a systematic study to unravel the synthesis of acetone, its propanal and propylene oxide isomers, as well as the propenol tautomers in interstellar analog ices composed of methane and acetaldehyde along with isotopic-substitution studies to trace the reaction pathways of the reactive intermediates. Chemical processes in the ices were triggered at 5.0 K upon exposure to proxies of Galactic cosmic rays in the form of energetic electrons. The products were detected isomer-selectively via vacuum ultraviolet (VUV) photoionization reflectron time-of-flight mass spectrometry. In our experiments, the branching ratio of acetone (CH3COCH3):propylene oxide (
- Publication Date:
- NSF-PAR ID:
- 10385820
- Journal Name:
- The Astrophysical Journal
- Volume:
- 941
- Issue:
- 2
- Page Range or eLocation-ID:
- Article No. 103
- ISSN:
- 0004-637X
- Publisher:
- DOI PREFIX: 10.3847
- Sponsoring Org:
- National Science Foundation
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Abstract -
Pure methane (CH 4 ) ices processed by energetic electrons under ultra-high vacuum conditions to simulate secondary electrons formed via galactic cosmic rays (GCRs) penetrating interstellar ice mantles have been shown to produce an array of complex hydrocarbons with the general formulae: C n H 2n+2 ( n = 4–8), C n H 2n ( n = 3–9), C n H 2n−2 ( n = 3–9), C n H 2n−4 ( n = 4–9), and C n H 2n−6 ( n = 6–7). By monitoring the in situ chemical evolution of the ice combined with temperature programmed desorption (TPD) studies and tunable single photon ionization coupled to a reflectron time-of-flight mass spectrometer, specific isomers of C 3 H 4 , C 3 H 6 , C 4 H 4 , and C 4 H 6 were probed. These experiments confirmed the synthesis of methylacetylene (CH 3 CCH), propene (CH 3 CHCH 2 ), cyclopropane (c-C 3 H 6 ), vinylacetylene (CH 2 CHCCH), 1-butyne (HCCC 2 H 5 ), 2-butyne (CH 3 CCCH 3 ), 1,2-butadiene (H 2 CCCH(CH 3 )), and 1,3-butadiene (CH 2 CHCHCH 2 ) with yields of 2.17 ± 0.95 × 10 −4 , 3.7 ±more »
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