skip to main content


Title: On the formation and the isomer specific detection of methylacetylene (CH 3 CCH), propene (CH 3 CHCH 2 ), cyclopropane (c-C 3 H 6 ), vinylacetylene (CH 2 CHCCH), and 1,3-butadiene (CH 2 CHCHCH 2 ) from interstellar methane ice analogues
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 ± 1.5 × 10 −3 , 1.23 ± 0.77 × 10 −4 , 1.28 ± 0.65 × 10 −4 , 4.01 ± 1.98 × 10 −5 , 1.97 ± 0.98 × 10 −4 , 1.90 ± 0.84 × 10 −5 , and 1.41 ± 0.72 × 10 −4 molecules eV −1 , respectively. Mechanistic studies exploring the formation routes of methylacetylene, propene, and vinylacetylene were also conducted, and revealed the additional formation of the 1,2,3-butatriene isomer. Several of the above isomers, methylacetylene, propene, vinylacetylene, and 1,3-butadiene, have repeatedly been shown to be important precursors in the formation of polycyclic aromatic hydrocarbons (PAHs), but until now their interstellar synthesis has remained elusive.  more » « less
Award ID(s):
1800975
NSF-PAR ID:
10157670
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
Volume:
21
Issue:
10
ISSN:
1463-9076
Page Range / eLocation ID:
5378 to 5393
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    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 (c-CH3CHOCH2):propanal (CH3CH2CHO) was determined to be (4.82 ± 0.05):(2.86 ± 0.13):1. The radical–radical recombination reaction leading to acetone emerged as the dominant channel. The propenols appeared only at a higher radiation dose via keto–enol tautomerization. The current study provides mechanistic information on the fundamental nonequilibrium pathways that may be responsible for the formation of acetone and its (enol) isomers inside the interstellar icy grains.

     
    more » « less
  2. We unravel, for the very first time, the formation pathways of hydroxyacetone (CH 3 COCH 2 OH), methyl acetate (CH 3 COOCH 3 ), and 3-hydroxypropanal (HCOCH 2 CH 2 OH), as well as their enol tautomers within mixed ices of methanol (CH 3 OH) and acetaldehyde (CH 3 CHO) analogous to interstellar ices in the ISM exposed to ionizing radiation at ultralow temperatures of 5 K. Exploiting photoionization reflectron time-of-flight mass spectrometry (PI-ReToF-MS) and isotopically labeled ices, the reaction products were selectively photoionized allowing for isomer discrimination during the temperature-programmed desorption phase. Based on the distinct mass-to-charge ratios and ionization energies of the identified species, we reveal the formation pathways of hydroxyacetone (CH 3 COCH 2 OH), methyl acetate (CH 3 COOCH 3 ), and 3-hydroxypropanal (HCOCH 2 CH 2 OH) via radical–radical recombination reactions and of their enol tautomers (prop-1-ene-1,2-diol (CH 3 C(OH)CHOH), prop-2-ene-1,2-diol (CH 2 C(OH)CH 2 OH), 1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) and prop-1-ene-1,3-diol (HOCH 2 CHCHOH)) via keto-enol tautomerization. To the best of our knowledge, 1-methoxyethen-1-ol (CH 3 OC(OH)CH 2 ) and prop-1-ene-1,3-diol (HOCH 2 CHCHOH) are experimentally identified for the first time. Our findings help to constrain the formation mechanism of hydroxyacetone and methyl acetate detected within star-forming regions and suggest that the hitherto astronomically unobserved isomer 3-hydroxypropanal and its enol tautomers represent promising candidates for future astronomical searches. These enol tautomers may contribute to the molecular synthesis of biologically relevant molecules in deep space due to their nucleophilic character and high reactivity. 
    more » « less
  3. Abstract We report a systematic study of all known methyl carbon chains toward TMC-1 using the second data release of the GOTHAM survey, as well as a search for larger species. Using Markov Chain Monte Carlo simulations and spectral line stacking of over 30 rotational transitions, we report statistically significant emission from methylcyanotriacetylene (CH 3 C 7 N) at a confidence level of 4.6 σ , and use it to derive a column density of ∼10 11 cm −2 . We also searched for the related species, methyltetraacetylene (CH 3 C 8 H), and place upper limits on the column density of this molecule. By carrying out the above statistical analyses for all other previously detected methyl-terminated carbon chains that have emission lines in our survey, we assess the abundances, excitation conditions, and formation chemistry of methylpolyynes (CH 3 C 2 n H) and methylcyanopolyynes (CH 3 C 2 n -1 N) in TMC-1, and compare those with predictions from a chemical model. Based on our observed trends in column density and relative populations of the A and E nuclear spin isomers, we find that the methylpolyyne and methylcyanopolyyne families exhibit stark differences from one another, pointing to separate interstellar formation pathways, which is confirmed through gas–grain chemical modeling with nautilus . 
    more » « less
  4. Abstract The precursors to larger, biologically relevant molecules are detected throughout interstellar space, but determining the presence and properties of these molecules during planet formation requires observations of protoplanetary disks at high angular resolution and sensitivity. Here, we present 0.″3 observations of HC 3 N, CH 3 CN, and c -C 3 H 2 in five protoplanetary disks observed as part of the Molecules with ALMA at Planet-forming Scales (MAPS) Large Program. We robustly detect all molecules in four of the disks (GM Aur, AS 209, HD 163296, and MWC 480) with tentative detections of c -C 3 H 2 and CH 3 CN in IM Lup. We observe a range of morphologies—central peaks, single or double rings—with no clear correlation in morphology between molecule or disk. Emission is generally compact and on scales comparable with the millimeter dust continuum. We perform both disk-integrated and radially resolved rotational diagram analysis to derive column densities and rotational temperatures. The latter reveals 5–10 times more column density in the inner 50–100 au of the disks when compared with the disk-integrated analysis. We demonstrate that CH 3 CN originates from lower relative heights in the disks when compared with HC 3 N, in some cases directly tracing the disk midplane. Finally, we find good agreement between the ratio of small to large nitriles in the outer disks and comets. Our results indicate that the protoplanetary disks studied here are host to significant reservoirs of large organic molecules, and that this planet- and comet-building material can be chemically similar to that in our own solar system. This paper is part of the MAPS special issue of the Astrophysical Journal Supplement. 
    more » « less
  5. Abstract

    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.

     
    more » « less