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Abstract Despite the organic molecule inventory detected in the Orion Kleinmann–Low Nebula (Orion KL), acetaldehyde (CH₃CHO)—one of the most ubiquitous interstellar aldehydes—has not been firmly identified with millimeter-wave interferometry. We analyze extensive Atacama Large Millimeter/submillimeter Array archival data sets (142–355 GHz) to search for acetaldehyde, revealing two distinct acetaldehyde emission peaks and one component with more complex kinematic structures. One peak aligns with MF10/IRc2, where emissions of other O-bearing complex organic molecules are rarely reported, while the other is coincident with the ethanol peak in the southwest region of the hot core. The MF10/IRc2 detection suggests unique chemistry, possibly influenced by repeated heating events. In contrast, codetection with ethanol indicates an ice origin and suggests a potential chemical relationship between the two species. We determine acetaldehyde column densities and kinetic temperatures toward these two peaks under local thermodynamic equilibrium assumptions and compare its distribution with ethanol and other molecules that have an aldehyde (HCO) group, such as methyl formate, glycolaldehyde, and formic acid. Toward the ethanol peak, the observed abundance ratios between HCO-containing species are analyzed using a chemical model. The model suggests two key points: (1) the destruction of ethanol to form acetaldehyde in the ice may contribute to the observed correlation between the two species; and (2) a long cold-collapse timescale and a methyl formate binding energy similar to or lower than water are needed to explain the observations. The relative abundance ratios obtained from the model are highly sensitive to the assumed kinetic temperature, which accounts for the high spatial variability of the aldehyde ratios observed toward Orion KL. 

Abstract Phosphorus is a key element that plays an essential role in biological processes important for living organisms on Earth. The origin and connection of phosphorus-bearing molecules to early solar system objects and star-forming molecular clouds is therefore of great interest, yet there are limited observations throughout different stages of low-mass (M < a few solar masses) star formation. Observations from the Yebes 40 m and IRAM 30 m telescopes detect for the first time in the 7 mm, 3 mm, and 2 mm bands multiple transitions of PN and PO, as well as a single transition of PO⁺, toward a low-mass starless core. The presence of PN, PO, and PO⁺is kinematically correlated with bright SiO(1–0) emission. Our results reveal not only that shocks are the main driver of releasing phosphorus from dust grains and into the gas phase but that the emission originates from gas not affiliated with the shock itself but quiescent gas that has been shocked in the recent past. From radiative transfer calculations, the PO/PN abundance ratio is found to be $3.1_{-0.6}^{+0.4}$, consistent with other high-mass and low-mass star-forming regions. This first detection of PO⁺toward any low-mass star-forming region reveals a PO⁺/PO ratio of $0.0115_{-0.0009}^{+0.0008}$, a factor of 10 lower than previously determined from observations of a Galactic center molecular cloud, suggesting its formation can occur under more standard Galactic cosmic-ray ionization rates. These results motivate the need for additional observations that can better disentangle the physical mechanisms and chemical drivers of this precursor of prebiotic chemistry. 

Abstract Gas-phase abundance ratios between C₂H₄O₂isomers methyl formate (MF), glycolaldehyde (GA), and acetic acid (AA) are typically on the order of 100:10:1 in star-forming regions. However, an unexplained divergence from this neat relationship was recently observed toward a collection of sources in the massive protocluster NGC 6334I; some sources exhibited extreme MF:GA ratios, producing a bimodal behavior between different sources, while the MF:AA ratio remained stable. Here, we use a three-phase gas-grain hot-core chemical model to study the effects of a large parameter space on the simulated C₂H₄O₂abundances. A combination of high gas densities and long timescales during ice-mantle desorption (∼125–160 K) appears to be the physical cause of the high MF:GA ratios. The main chemical mechanism for GA destruction occurring under these conditions is the rapid adsorption and reaction of atomic H with GA on the ice surfaces before it has time to desorb. The different binding energies of MF and GA on water ice are crucial to the selectivity of the surface destruction mechanism; individual MF molecules rapidly escape the surface when exposed by water loss, while GA lingers and is destroyed by H. Moderately elevated cosmic-ray ionization rates can increase absolute levels of “complex organic molecule” (COM) production in the ices and increase the MF:GA ratio, but extreme values are destructive for gas-phase COMs. We speculate that the high densities required for extreme MF:GA ratios could be evidence of COM emission dominated by COMs desorbing within a circumstellar disk. 

Context. Hot molecular cores correspond to the phase of star formation during which many molecules, in particular complex organic molecules (COMs), thermally desorb from the surface of dust grains. Sophisticated kinetic models of interstellar chemistry describe the processes that lead to the formation and subsequent evolution of COMs in star-forming regions. Aims. Our goal is to derive the chemical composition of hot cores in order to improve our understanding of interstellar chemistry. In particular, we want to test the models by comparing their predictions to the observed composition of the gas phase of hot cores. Methods. We used the Atacama Large Millimeter/submillimeter Array (ALMA) to perform an imaging spectral line survey of the high mass star-forming region Sagittarius B2(N) at 3 mm, called Re-exploring Molecular Complexity with ALMA (ReMoCA). We modeled under the assumption of local thermodynamic equilibrium the spectra obtained with this survey toward the sources embedded in the secondary hot core Sgr B2(N2). We compared the chemical composition of these sources to that of sources from the literature and to predictions of the chemical kinetics model MAGICKAL. Results. We detected up to 58 molecules toward Sgr B2(N2)’s hot cores, including up to 24 COMs, as well as many less abundant isotopologs. The compositions of some pairs of sources are well correlated, but differences also exist, in particular for HNCO and NH₂CHO. The abundances of series of homologous molecules drop by about one order of magnitude at each further step in complexity. The nondetection of radicals yields stringent constraints on the models. The comparison to the chemical models confirms previous evidence of a high cosmic-ray ionization rate in Sgr B2(N). The comparison to sources from the literature gives a new insight into chemical differentiation. The composition of most hot cores of Sgr B2(N2) is tightly correlated to that of the hot core G31.41+0.31 and the hot corino IRAS 16293–2422 B after normalizing the abundances by classes of molecules (O-bearing, N-bearing, O+N-bearing, and S-bearing). There is no overall correlation between Sgr B2(N2) and the shocked region G+0.693−0.027 also located in Sgr B2, and even less with the cold starless core TMC-1. The class of N-bearing species reveals the largest variance among the four classes of molecules. The S-bearing class shows in contrast the smallest variance. Conclusions. These results imply that the class of N-bearing molecules reacts more sensitively to shocks, low-temperature gas phase chemistry after nonthermal desorption, or density. The overall abundance shifts observed between the N-bearing and O-bearing molecules may indicate how violently and completely the ice mantles are desorbed. 

Context.Acetone (CH₃COCH₃) is one of the most abundant three-carbon oxygen-bearing complex organic molecules (O-COMs) that have been detected in space. The previous detections were made in the gas phase toward star-forming regions that are chemically rich, mostly in protostellar systems. Recently, acetone ice has also been reported as (tentatively) detected toward two low-mass protostars, allowing comparisons in acetone abundances between gas and ice. The detection of acetone ice warrants a more systematic study of its gaseous abundances which is currently lacking. Aims.We aim to measure the gas-phase abundances of acetone in a large sample obtained from the CoCCoA program, and investigate the chemical evolution of acetone from ice to gas in protostellar systems. Methods.We fit the ALMA spectra to determine the column density, excitation temperature, and line width of acetone in 12 high-mass protostars as part of CoCCoA. We also constrained the physical properties of propanal (C₂H₅CHO), ketene (CH₂CO), and propyne (CH₃CCH), which might be chemically linked with acetone. We discuss the possible formation pathways of acetone by making comparisons in its abundances between gas and ice and between observations and simulations. Results.We firmly detect acetone, ketene, and propyne in the 12 high-mass protostars. The observed gas-phase abundances of acetone are surprisingly high compared to those of two-carbon O-COMs (especially aldehydes). Propanal is considered as tentatively detected due to lack of unblended lines covered in our data. The derived physical properties suggest that acetone, propanal, and ketene have the same origin from hot cores as other O-COMs, while propyne tends to trace the more extended outflows. The acetone-to-methanol ratios are higher in the solid phase than in the gas phase by one order of magnitude, which suggests gas-phase reprocessing after sublimation. There are several suggested formation pathways of acetone (in both ice and gas) from acetaldehyde, ketene, and propylene. The observed ratios between acetone and these three species are rather constant across the sample, and can be well reproduced by astrochemical simulations. Conclusions.On the one hand, the observed high gas-phase abundances of acetone along with dimethyl ether (CH₃OCH₃) and methyl formate (CH₃OCHO) may hint at specific chemical mechanisms that favor the production of ethers, esters, and ketones over alcohols and aldehydes. On the other hand, the overall low gas-phase abundances of aldehydes may result from destruction pathways that are overlooked or underestimated in previous studies. The discussed formation pathways of acetone from acetaldehyde, ketene, and propylene seem plausible from observations and simulations, but more investigations are needed to draw more solid conclusions. We emphasize the importance of studying acetone, which is an abundant COM that deserves more attention in the future. 

Context.Recent JWST observations have measured the ice chemical composition towards two highly extinguished background stars, NIR38 and J110621, in the Chamaeleon I molecular cloud. The observed excess of extinction on the long-wavelength side of the H₂O ice band at 3 μm has been attributed to a mixture of CH₃OH with ammonia hydrates NH₃·H₂O), which suggests that CH₃OH ice in this cloud could have formed in a water-rich environment with little CO depletion. Laboratory experiments and quantum chemical calculations suggest that CH₃OH could form via the grain surface reactions CH₃+ OH and/or C + H₂O in water-rich ices. However, no dedicated chemical modelling has been carried out thus far to test their efficiency. In addition, it remains unexplored how the efficiencies of the proposed mechanisms depend on the astrochemical code employed. Aims.We modelled the ice chemistry in the Chamaeleon I cloud to establish the dominant formation processes of CH₃OH, CO, CO₂, and of the hydrides CH₄and NH₃(in addition to H₂O). By using a set of state-of-the-art astrochemical codes (MAGICKAL, MONACO, Nautilus, UCLCHEM, and KMC simulations), we can test the effects of the different code architectures (rate equation vs. stochastic codes) and of the assumed ice chemistry (diffusive vs. non-diffusive). Methods.We consider a grid of models with different gas densities, dust temperatures, visual extinctions, and cloud-collapse length scales. In addition to the successive hydrogenation of CO, the codes’ chemical networks have been augmented to include the alternative processes for CH₃OH ice formation in water-rich environments (i.e. the reactions CH₃+ OH → CH₃OH and C + H₂O → H₂CO). Results.Our models show that the JWST ice observations are better reproduced for gas densities ≥10⁵cm⁻³and collapse timescales ≥10⁵yr. CH₃OH ice formation occurs predominantly (>99%) via CO hydrogenation. The contribution of reactions CH₃+ OH and C + H₂O is negligible. The CO₂ice may form either via CO + OH or CO + O depending on the code. However, KMC simulations reveal that both mechanisms are efficient despite the low rate of the CO + O surface reaction. CH₄is largely underproduced for all codes except for UCLCHEM, for which a higher amount of atomic C is available during the translucent cloud phase of the models. Large differences in the predicted abundances are found at very low dust temperatures (T_dust<12 K) between diffusive and non-diffusive chemistry codes. This is due to the fact that non-diffusive chemistry takes over diffusive chemistry at such low T_dust. This could explain the rather constant ice chemical composition found in Chamaeleon I and other dense cores despite the different visual extinctions probed. 

Context. The solid-state reaction C + H₂O → H₂CO has recently been studied experimentally and claimed as a new ‘non-energetic’ pathway to complex organic and prebiotic molecules in cold astrophysical environments. Aims. We compared results of astrochemical network modelling with and without the C + H₂O surface reaction. Methods. A typical, generic collapse model in which a dense core forms from initially diffuse conditions was used along with the astrochemical kinetics model MAGICKAL. Results. The inclusion of the reaction does not notably enhance the abundance of formaldehyde itself; however, it significantly enhances the abundance of methanol (formed by the hydrogenation of formaldehyde) on the dust grains at early times, when the high gas-phase abundance of atomic C leads to relatively rapid adsorption onto the grain surfaces. As a result, the gas-phase abundance of methanol is also increased due to chemical desorption, quickly reaching abundances close to ∼10⁻⁹n_H, which decline strongly under late-time, high-density conditions. The reaction also influences the abundances of simple ice species, with the CO₂abundance increased in the earliest, deepest ice layers, while the water-ice abundance is somewhat depressed. The abundances of various complex organic molecules are also affected, with some species becoming more abundant and others less. When gas-phase atomic carbon becomes depleted, the grain-surface chemistry returns to behaviour that would be expected if there had been no new reaction. Conclusions. Our results show that fundamental reactions involving the simplest atomic and molecular species can be of great importance for the evolution of astrochemical reaction networks, thus providing motivation for future experimental and theoretical studies. 

Context.Complex organic molecules (COMs) have been detected ubiquitously in protostellar systems. However, at shorter wavelengths (~0.8 mm), it is generally more difficult to detect larger molecules than at longer wavelengths (~3 mm) because of the increase in millimeter dust opacity, line confusion, and unfavorable partition function. Aims.We aim to search for large molecules (more than eight atoms) in the Atacama Large Millimeter/submillimeter Array (ALMA) Band 3 spectrum of IRAS 16293-2422 B. In particular, the goal is to quantify the usability of ALMA Band 3 for molecular line surveys in comparison to similar studies at shorter wavelengths. Methods.We used deep ALMA Band 3 observations of IRAS 16293-2422 B to search for more than 70 molecules and identified as many lines as possible in the spectrum. The spectral settings were set to specifically target three-carbon species such as i- and n-propanol and glycerol, the next step after glycolaldehyde and ethylene glycol in the hydrogenation of CO. We then derived the column densities and excitation temperatures of the detected species and compared the ratios with respect to methanol between Band 3 (~3 mm) and Band 7 (~1 mm, Protostellar Interferometric Line Survey) observations of this source to examine the effect of the dust optical depth. Results.We identified lines of 31 molecules including many oxygen-bearing COMs such as CH₃OH, CH₂OHCHO, CH₃CH₂OH, and c-C₂H₄O and a few nitrogen- and sulfur-bearing ones such as HOCH₂CN and CH₃SH. The largest detected molecules are gGg-(CH₂OH)₂and CH₃COCH₃. We did not detect glycerol or i- and n-propanol, but we do provide upper limits for them which are in line with previous laboratory and observational studies. The line density in Band 3 is only ~2.5 times lower in frequency space than in Band 7. From the detected lines in Band 3 at a ≳ 6σ level, ~25–30% of them could not be identified indicating the need for more laboratory data of rotational spectra. We find similar column densities and column density ratios of COMs (within a factor ~2) between Band 3 and Band 7. Conclusions.The effect of the dust optical depth for IRAS 16293-2422 B at an off-source location on column densities and column density ratios is minimal. Moreover, for warm protostars, long wavelength spectra (~3 mm) are not only crowded and complex, but they also take significantly longer integration times than shorter wavelength observations (~0.8 mm) to reach the same sensitivity limit. The 3 mm search has not yet resulted in the detection of larger and more complex molecules in warm sources. A full deep ALMA Band 2–3 (i.e., ~3–4 mm wavelengths) survey is needed to assess whether low frequency data have the potential to reveal more complex molecules in warm sources.