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Jørgensen, Jes K., Arnaud Belloche y Robin T. Garrod. "Astrochemistry During the Formation of Stars". Annual Review of Astronomy and Astrophysics 58, n.º 1 (18 de agosto de 2020): 727–78. http://dx.doi.org/10.1146/annurev-astro-032620-021927.
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Star-forming regions show a rich and varied chemistry, including the presence of complex organic molecules—in both the cold gas distributed on large scales and the hot regions close to young stars where protoplanetary disks arise. Recent advances in observational techniques have opened new possibilities for studying this chemistry. In particular, the Atacama Large Millimeter/submillimeter Array has made it possible to study astrochemistry down to Solar System–size scales while also revealing molecules of increasing variety and complexity. In this review, we discuss recent observations of the chemistry of star-forming environments, with a particular focus on complex organic molecules, taking context from the laboratory experiments and chemical models that they have stimulated. The key takeaway points include the following: ▪ The physical evolution of individual sources plays a crucial role in their inferred chemical signatures and remains an important area for observations and models to elucidate. ▪ Comparisons of the abundances measured toward different star-forming environments (high-mass versus low-mass, Galactic Center versus Galactic disk) reveal a remarkable similarity, which is an indication that the underlying chemistry is relatively independent of variations in their physical conditions. ▪ Studies of molecular isotopologues in star-forming regions provide a link with measurements in our own Solar System, and thus may shed light on the chemical similarities and differences expected in other planetary systems.
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Qin, Sheng-Li, Tie Liu, Xunchuan Liu, Paul F. Goldsmith, Di Li, Qizhou Zhang, Hong-Li Liu et al. "ATOMS: ALMA Three-millimeter Observations of Massive Star-forming regions – VIII. A search for hot cores by using C2H5CN, CH3OCHO, and CH3OH lines". Monthly Notices of the Royal Astronomical Society 511, n.º 3 (29 de enero de 2022): 3463–76. http://dx.doi.org/10.1093/mnras/stac219.
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ABSTRACT Hot cores characterized by rich lines of complex organic molecules are considered as ideal sites for investigating the physical and chemical environments of massive star formation. We present a search for hot cores by using typical nitrogen- and oxygen-bearing complex organic molecules (C2H5CN, CH3OCHO, and CH3OH), based on ALMA Three-millimeter Observations of Massive Star-forming regions (ATOMS). The angular resolutions and line sensitivities of the ALMA observations are better than 2 arcsec and 10 mJy beam−1, respectively. A total of 60 hot cores are identified with 45 being newly detected, in which the complex organic molecules have high gas temperatures (> 100 K) and hot cores have small source sizes (< 0.1 pc). So far, this is the largest sample of hot cores observed with similar angular resolution and spectral coverage. The observations have also shown nitrogen and oxygen differentiation in both line emission and gas distribution in 29 hot cores. Column densities of CH3OH and CH3OCHO increase as rotation temperatures rise. The column density of CH3OCHO correlates tightly with that of CH3OH. The pathways for production of different species are discussed. Based on the spatial position difference between hot cores and ultracompact H ii (UC H ii) regions, we conclude that 24 hot cores are externally heated, while the other hot cores are internally heated. The observations presented here will potentially help establish a hot core template for studying massive star formation and astrochemistry.
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Jørgensen, Jes K. "The ALMA-PILS Survey: New insights into the complex chemistry of young stars". Proceedings of the International Astronomical Union 14, S345 (agosto de 2018): 132–36. http://dx.doi.org/10.1017/s1743921319002849.
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AbstractUnderstanding how, when and where complex organic and potentially prebiotic molecules are formed is a fundamental goal of astrochemistry. Since its beginning the Atacama Large Millimeter/submillimeter Array (ALMA) has demonstrated its capabilities for studies of the chemistry of solar-type stars. Its high sensitivity and fine spectral and angular resolution makes it possible to study the chemistry of young stars on Solar System scales. We here present an unbiased spectral survey, Protostellar Interferometric Line Survey (PILS), of the astrochemical template source and Class 0 protostellar binary IRAS 16293-2422 using ALMA. The high quality ALMA data have allowed us to detect a wealth of species previously undetected toward solar-type protostars as well as the interstellar medium in general. Also, the data show the presence of numerous rare isotopologues of complex organic molecules and other species: the exact measurements of the abundances of the complex organic molecules and their isotopologues shed new light onto the formation of these species and provide a chemical link between the embedded protostellar stages and the early Solar System.
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Yang, Yao-Lun, Joel D. Green, Klaus M. Pontoppidan, Jennifer B. Bergner, L. Ilsedore Cleeves, Neal J. Evans II, Robin T. Garrod et al. "CORINOS. I. JWST/MIRI Spectroscopy and Imaging of a Class 0 Protostar IRAS 15398–3359". Astrophysical Journal Letters 941, n.º 1 (1 de diciembre de 2022): L13. http://dx.doi.org/10.3847/2041-8213/aca289.
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Abstract The origin of complex organic molecules (COMs) in young Class 0 protostars has been one of the major questions in astrochemistry and star formation. While COMs are thought to form on icy dust grains via gas-grain chemistry, observational constraints on their formation pathways have been limited to gas-phase detection. Sensitive mid-infrared spectroscopy with JWST enables unprecedented investigation of COM formation by measuring their ice absorption features. Mid-infrared emission from disks and outflows provide complementary constraints on the protostellar systems. We present an overview of JWST/Mid-Infrared Instrument (MIRI) Medium Resolution Spectroscopy (MRS) and imaging of a young Class 0 protostar, IRAS 15398−3359, and identify several major solid-state absorption features in the 4.9–28 μm wavelength range. These can be attributed to common ice species, such as H2O, CH3OH, NH3, and CH4, and may have contributions from more complex organic species, such as C2H5OH and CH3CHO. In addition to ice features, the MRS spectra show many weaker emission lines at 6–8 μm, which are due to warm CO gas and water vapor, possibly from a young embedded disk previously unseen. Finally, we detect emission lines from [Fe ii], [Ne ii], [S i], and H2, tracing a bipolar jet and outflow cavities. MIRI imaging serendipitously covers the southwestern (blueshifted) outflow lobe of IRAS 15398−3359, showing four shell-like structures similar to the outflows traced by molecular emission at submillimeter wavelengths. This overview analysis highlights the vast potential of JWST/MIRI observations and previews scientific discoveries in the coming years.
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Ioppolo, S., B. A. McGuire, M. A. Allodi y G. A. Blake. "THz and mid-IR spectroscopy of interstellar ice analogs: methyl and carboxylic acid groups". Faraday Discuss. 168 (2014): 461–84. http://dx.doi.org/10.1039/c3fd00154g.
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A fundamental problem in astrochemistry concerns the synthesis and survival of complex organic molecules (COMs) throughout the process of star and planet formation. While it is generally accepted that most complex molecules and prebiotic species form in the solid phase on icy grain particles, a complete understanding of the formation pathways is still largely lacking. To take full advantage of the enormous number of available THz observations (e.g.,Herschel Space Observatory, SOFIA, and ALMA), laboratory analogs must be studied systematically. Here, we present the THz (0.3–7.5 THz; 10–250 cm−1) and mid–IR (400–4000 cm−1) spectra of astrophysically-relevant species that share the same functional groups, including formic acid (HCOOH) and acetic acid (CH3COOH), and acetaldehyde (CH3CHO) and acetone ((CH3)2CO), compared to more abundant interstellar molecules such as water (H2O), methanol (CH3OH), and carbon monoxide (CO). A suite of pure and mixed binary ices are discussed. The effects on the spectra due to the composition and the structure of the ice at different temperatures are shown. Our results demonstrate that THz spectra are sensitive to reversible and irreversible transformations within the ice caused by thermal processing, suggesting that THz spectra can be used to study the composition, structure, and thermal history of interstellar ices. Moreover, the THz spectrum of an individual species depends on the functional group(s) within that molecule. Thus, future THz studies of different functional groups will help in characterizing the chemistry and physics of the interstellar medium (ISM).
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Mininni, C., M. T. Beltrán, V. M. Rivilla, A. Sánchez-Monge, F. Fontani, T. Möller, R. Cesaroni et al. "The GUAPOS project: G31.41+0.31 Unbiased ALMA sPectral Observational Survey". Astronomy & Astrophysics 644 (diciembre de 2020): A84. http://dx.doi.org/10.1051/0004-6361/202038966.
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Context. One of the goals of astrochemistry is to understand the degree of chemical complexity that can be reached in star-forming regions, along with the identification of precursors of the building blocks of life in the interstellar medium. To answer such questions, unbiased spectral surveys with large bandwidth and high spectral resolution are needed, in particular, to resolve line blending in chemically rich sources and identify each molecule (especially for complex organic molecules). These kinds of observations have already been successfully carried out, primarily towards the Galactic Center, a region that shows peculiar environmental conditions. Aims. We present an unbiased spectral survey of one of the most chemically rich hot molecular cores located outside the Galactic Center, in the high-mass star-forming region G31.41+0.31. The aim of this 3mm spectral survey is to identify and characterize the physical parameters of the gas emission in different molecular species, focusing on complex organic molecules. In this first paper, we present the survey and discuss the detection and relative abundances of the three isomers of C2H4O2: methyl formate, glycolaldehyde, and acetic acid. Methods. Observations were carried out with the ALMA interferometer, covering all of band 3 from 84 to 116 GHz (~32 GHz bandwidth) with an angular resolution of 1.2′′ × 1.2′′ (~ 4400 au × 4400 au) and a spectral resolution of ~0.488 MHz (~1.3−1.7 km s−1). The transitions of the three molecules have been analyzed with the software XCLASS to determine the physical parameters of the emitted gas. Results. All three isomers were detected with abundances of (2 ± 0.6) × 10−7, (4.3−8) × 10−8, and (5.0 ± 1.4) × 10−9 for methyl formate, acetic acid, and glycolaldehyde, respectively. Methyl formate and acetic acid abundances are the highest detected up to now, if compared to sources in the literature. The size of the emission varies among the three isomers with acetic acid showing the most compact emission while methyl formate exhibits the most extended emission. Different chemical pathways, involving both grain-surface chemistry and cold or hot gas-phase reactions, have been proposed for the formation of these molecules, but the small number of detections, especially of acetic acid and glycolaldehyde, have made it very difficult to confirm or discard the predictions of the models. The comparison with chemical models in literature suggests the necessity of grain-surface routes for the formation of methyl formate in G31, while for glycolaldehyde both scenarios could be feasible. The proposed grain-surface reaction for acetic acid is not capable of reproducing the observed abundance in this work, while the gas-phase scenario should be further tested, given the large uncertainties involved.
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López-Sepulcre, Ana y Mathilde Bouvier. "Molecular richness in protostars: Lessons learnt from spectral observations". EPJ Web of Conferences 265 (2022): 00026. http://dx.doi.org/10.1051/epjconf/202226500026.
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The gas associated with the early stages of star formation contains traces of a large variety of molecular species, many of which are organic in nature. Interestingly, we observe a substantial chemical diversity among protostars, with some objects being enriched in what astrochemists label interstellar complex organic molecules (iCOMs), such as methyl formate (HCOOCH3), while others are overabundant in unsaturated carbon chains such as C4H. What is the cause of this diversity? And where should we place the proto-solar-system in this chemical context: was it rich in iCOMs, or in carbon chains, or in both? Thanks to the development of sensitive broadband (sub-)millimetre instrumentation, both in single-dish telescopes and interferometers, we are currently witnessing big steps forward in this area. The present contribution summarises what we have learnt, in the past decade or so, about the molecular contents in solar-mass protostellar sources, and suggests a few guidelines to stimulate progress in the field.
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García-Hernández, D. Anibal. "Molecular processes from the AGB to the PN stage". Proceedings of the International Astronomical Union 7, S283 (julio de 2011): 148–55. http://dx.doi.org/10.1017/s1743921312010861.
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AbstractMany complex organic molecules and inorganic solid-state compounds have been observed in the circumstellar shell of stars (both C-rich and O-rich) in the transition phase between Asymptotic Giant Branch (AGB) stars and Planetary Nebulae (PNe). This short (~102-104 years) phase of stellar evolution represents a wonderful laboratory for astrochemistry and provides severe constraints on any model of gas-phase and solid-state chemistry. One of the major challenges of present day astrophysics and astrochemistry is to understand the formation pathways of these complex organic molecules and inorganic solid-state compounds (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene in the case of a C-rich chemistry and oxides and crystalline silicates in O-rich environments) in space. In this review, I present an observational review of the molecular processes in the late stages of stellar evolution with a special emphasis on the first detections of fullerenes and graphene in PNe.
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Garrod, Robin T., Susanna L. Widicus Weaver y Eric Herbst. "Complex chemistry in star-forming regions". Proceedings of the International Astronomical Union 4, S251 (febrero de 2008): 123–24. http://dx.doi.org/10.1017/s1743921308021339.
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AbstractWe present a new gas-grain chemical model that allows the grain-surface formation of saturated, complex, organic species from their constituent functional-groups–basic building blocks that derive from the cosmic ray-induced photodissociation of the granular ice mantles. The surface mobility of the funtional-group radicals is crucial to the reactions, and much of the formation of complex molecules occurs at the intermediate temperatures (~20–40 K) attained during the warm-up of the hot core. Our model traces the evolution of a large range of detected, and as yet un-detected, complex molecules.
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Öberg, Karin I., Trish Lauck y Dawn Graninger. "COMPLEX ORGANIC MOLECULES DURING LOW-MASS STAR FORMATION: PILOT SURVEY RESULTS". Astrophysical Journal 788, n.º 1 (22 de mayo de 2014): 68. http://dx.doi.org/10.1088/0004-637x/788/1/68.
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Fulvio, Daniele, Alexey Potapov, Jiao He y Thomas Henning. "Astrochemical Pathways to Complex Organic and Prebiotic Molecules: Experimental Perspectives for In Situ Solid-State Studies". Life 11, n.º 6 (17 de junio de 2021): 568. http://dx.doi.org/10.3390/life11060568.
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A deep understanding of the origin of life requires the physical, chemical, and biological study of prebiotic systems and the comprehension of the mechanisms underlying their evolutionary steps. In this context, great attention is paid to the class of interstellar molecules known as “Complex Organic Molecules” (COMs), considered as possible precursors of prebiotic species. Although COMs have already been detected in different astrophysical environments (such as interstellar clouds, protostars, and protoplanetary disks) and in comets, the physical–chemical mechanisms underlying their formation are not yet fully understood. In this framework, a unique contribution comes from laboratory experiments specifically designed to mimic the conditions found in space. We present a review of experimental studies on the formation and evolution of COMs in the solid state, i.e., within ices of astrophysical interest, devoting special attention to the in situ detection and analysis techniques commonly used in laboratory astrochemistry. We discuss their main strengths and weaknesses and provide a perspective view on novel techniques, which may help in overcoming the current experimental challenges.
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Kuan, Y. J., H. C. Huang, S. B. Charnley, W. L. Tseng, L. E. Snyder, P. Ehrenfreund, Z. Kisiel, S. Thorwirth, R. K. Bohn y T. L. Wilson. "Prebiologically Important Interstellar Molecules". Symposium - International Astronomical Union 213 (2004): 185–88. http://dx.doi.org/10.1017/s0074180900193246.
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Understanding the organic chemistry of molecular clouds, particularly the formation of biologically important molecules, is fundamental to the study of the processes which lead to the origin, evolution and distribution of life in the Galaxy. Determining the level of molecular complexity attainable in the clouds, and the nature of the complex organic material available to protostellar disks and the planetary systems that form from them, requires an understanding of the possible chemical pathways and is therefore a central question in astrochemistry. We have thus searched for prebiologically important molecules in the hot molecular cloud cores: Sgr B2(N-LMH), W51 e1/e2 and Orion-KL. Among the molecules searched: Pyrimidine is the unsubstituted ring analogue for three of the DNA and RNA bases. 2H-Azirine and Aziridine are azaheterocyclic compounds. And Glycine is the simplest amino acid. Detections of these interstellar organic molecular species will thus have important implications for Astrobiology. Our preliminary results indicate a tentative detection of interstellar glycine. If confirmed, this will be the first detection of an amino acid in interstellar space and will greatly strengthen the thesis that interstellar organic molecules could have played a pivotal role in the prebiotic chemistry of the early Earth.
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van Gelder, M. L., B. Tabone, Ł. Tychoniec, E. F. van Dishoeck, H. Beuther, A. C. A. Boogert, A. Caratti o Garatti et al. "Complex organic molecules in low-mass protostars on Solar System scales". Astronomy & Astrophysics 639 (julio de 2020): A87. http://dx.doi.org/10.1051/0004-6361/202037758.
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Context. Complex organic molecules (COMs) are thought to form on icy dust grains in the earliest phase of star formation. The evolution of these COMs from the youngest Class 0/I protostellar phases toward the more evolved Class II phase is still not fully understood. Since planet formation seems to start early, and mature disks are too cold for characteristic COM emission lines, studying the inventory of COMs on Solar- System scales in the Class 0/I stage is relevant. Aims. Our aim is to determine the abundance ratios of oxygen-bearing COMs in Class 0 protostellar systems on scales of ~100 AU radius. We aim to compare these abundances with one another, and to the abundances of other low-mass protostars such as IRAS 16293-2422B and HH 212. Additionally, using both cold and hot COM lines, the gas-phase abundances can be tracked from a cold to a hot component, and ultimately be compared with those in ices to be measured with the James Webb Space Telescope (JWST). The abundance of deuterated methanol allows us to probe the ambient temperature during the formation of this species. Methods. ALMA Band 3 (3 mm) and Band 6 (1 mm) observations are obtained for seven Class 0 protostars in the Perseus and Serpens star-forming regions. By modeling the inner protostellar region using local thermodynamic equilibrium models, the excitation temperature and column densities are determined for several O-bearing COMs including methanol (CH3OH), acetaldehyde (CH3CHO), methyl formate (CH3OCHO), and dimethyl ether (CH3OCH3). Abundance ratios are taken with respect to CH3OH. Results. Three out of the seven of the observed sources, B1-c, B1-bS (both Perseus), and Serpens S68N (Serpens), show COM emission. No clear correlation seems to exist between the occurrence of COMs and source luminosity. The abundances of several COMs such as CH3OCHO, CH3OCH3, acetone (CH3COCH3), and ethylene glycol ((CH2OH)2) are remarkably similar for the three COM-rich sources; this similarity also extends to IRAS 16293-2422B and HH 212, even though collectively these sources originate from four different star-forming regions (i.e., Perseus, Serpens, Ophiuchus, and Orion). For other COMs like CH3CHO, ethanol (CH3CH2OH), and glycolaldehyde (CH2OHCHO), the abundances differ by up to an order of magnitude, indicating that local source conditions become important. B1-c hosts a cold (Tex ≈ 60 K), more extended component of COM emission with a column density of typically a few percent of the warm/hot (Tex ~ 200 K) central component. A D/H ratio of 1–3% is derived for B1-c, S68N, and B1-bS based on the CH2DOH/CH3OH ratio (taking into account statistical weighting) suggesting a temperature of ~15 K during the formation of methanol. This ratio is consistent with other low-mass protostars, but is lower than for high-mass star-forming regions. Conclusions. The abundance ratios of most O-bearing COMs are roughly fixed between different star-forming regions, and are presumably set at an earlier cold prestellar phase. For several COMs, local source properties become important. Future mid-infrared facilities such as JWST/MIRI will be essential for the direct observation of COM ices. Combining this with a larger sample of COM-rich sources with ALMA will allow ice and gas-phase abundances to be directly linked in order to constrain the routes that produce and maintain chemical complexity during the star formation process.
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Scibelli, Samantha, Yancy Shirley, Anton Vasyunin y Ralf Launhardt. "Detection of complex organic molecules in young starless core L1521E". Monthly Notices of the Royal Astronomical Society 504, n.º 4 (23 de abril de 2021): 5754–67. http://dx.doi.org/10.1093/mnras/stab1151.
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ABSTRACT Determining the level of chemical complexity within dense starless and gravitationally bound pre-stellar cores is crucial for constructing chemical models, which subsequently constrain the initial chemical conditions of star formation. We have searched for complex organic molecules (COMs) in the young starless core L1521E, and report the first clear detection of dimethyl ether (CH3OCH3), methyl formate (HCOOCH3), and vinyl cyanide (CH2CHCN). Eight transitions of acetaldehyde (CH3CHO) were also detected, five of which (A states) were used to determine an excitation temperature to then calculate column densities for the other oxygen-bearing COMs. If source size was not taken into account (i.e. if filling fraction was assumed to be one), column density was underestimated, and thus we stress the need for higher resolution mapping data. We calculated L1521E COM abundances and compared them to other stages of low-mass star formation, also finding similarities to other starless/pre-stellar cores, suggesting related chemical evolution. The scenario that assumes formation of COMs in gas-phase reactions between precursors formed on grains and then ejected to the cold gas via reactive desorption was tested and was unable to reproduce observed COM abundances, with the exception of CH3CHO. These results suggest that COMs observed in cold gas are formed not by gas-phase reactions alone, but also through surface reactions on interstellar grains. Our observations present a new, unique challenge for existing theoretical astrochemical models.
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Rivilla, V. M., M. T. Beltrán, R. Cesaroni, F. Fontani, C. Codella y Q. Zhang. "Formation of ethylene glycol and other complex organic molecules in star-forming regions". Astronomy & Astrophysics 598 (febrero de 2017): A59. http://dx.doi.org/10.1051/0004-6361/201628373.
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Coletta, A., F. Fontani, V. M. Rivilla, C. Mininni, L. Colzi, Á. Sánchez-Monge y M. T. Beltrán. "Evolutionary study of complex organic molecules in high-mass star-forming regions". Astronomy & Astrophysics 641 (septiembre de 2020): A54. http://dx.doi.org/10.1051/0004-6361/202038212.
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We have studied four complex organic molecules (COMs), the oxygen-bearing methyl formate (CH3OCHO) and dimethyl ether (CH3OCH3) as well as the nitrogen-bearing formamide (NH2CHO) and ethyl cyanide (C2H5CN), towards a large sample of 39 high-mass star-forming regions representing different evolutionary stages, from early to evolved phases. We aim to identify potential correlations and chemical links between the molecules and to trace their evolutionary sequence through the star formation process. We analysed spectra obtained at 3, 2, and 0.9 mm with the IRAM-30m telescope. We derived the main physical parameters for each species by fitting the molecular lines. We compared them and evaluated their evolution while also taking several other interstellar environments into account. We report detections in 20 sources, revealing a clear dust absorption effect on column densities. Derived abundances range between ~ 10−10−10−7 for CH3OCHO and CH3OCH3, ~ 10−12−10−10 for NH2CHO, and ~ 10−11−10−9 for C2H5CN. The abundances of CH3OCHO, CH3OCH3, and C2H5CN are very strongly correlated (r ≥ 0.92) across ~ 4 orders of magnitude. We note that CH3OCHO and CH3OCH3 show the strongest correlations in most parameters, and a nearly constant ratio (~ 1) over a remarkable ~ 9 orders of magnitude in luminosity for the following wide variety of sources: pre-stellar to evolved cores, low- to high-mass objects, shocks, Galactic clouds, and comets. This indicates that COMs chemistry is likely early developed and then preserved through evolved phases. Moreover, the molecular abundances clearly increase with evolution, covering ~ 6 orders of magnitude in the luminosity/mass ratio. We consider CH3OCHO and CH3OCH3 to be most likely chemically linked. They could, for example, share a common precursor, or be formed one from the other. Based on correlations, ratios, and the evolutionary trend, we propose a general scenario for all COMs, involving a formation in the cold, earliest phases of star formation and a following increasing desorption with the progressive thermal and shock-induced heating of the evolving core.
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Schuessler, Caden, Anthony Remijan, Ci Xue, Joshua Carder, Haley Scolati y Brett McGuire. "Searching for Propionamide (C2H5CONH2) toward Sagittarius B2 at Centimeter Wavelengths". Astrophysical Journal 941, n.º 1 (1 de diciembre de 2022): 102. http://dx.doi.org/10.3847/1538-4357/ac8668.
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Abstract The formation of molecules in the interstellar medium (ISM) remains a complex and unresolved question in astrochemistry. A group of molecules of particular interest involves the linkage between a carboxyl and amine group, similar to that of a peptide bond. The detection of molecules containing these peptide-like bonds in the ISM can help elucidate possible formation mechanisms, as well as indicate the level of molecular complexity available within certain regions of the ISM. Two of the simplest molecules containing a peptide-like bond, formamide (NH2CHO) and acetamide (CH3CONH2), have previously been detected toward the star-forming region Sagittarius B2 (Sgr B2). Recently, the interstellar detection of propionamide (C2H5CONH2) was reported toward Sgr B2(N) with Atacama Large Millimeter/submillimeter Array (ALMA) observations at millimeter wavelengths. Yet, this detection has been questioned by others from the same set of ALMA observations as no statistically significant line emission was identified from any uncontaminated transitions. Using the Prebiotic Interstellar Molecule Survey (PRIMOS) observations, we report an additional search for C2H5CONH2 at centimeter wavelengths conducted with the Green Bank Telescope. No spectral signatures of C2H5CONH2 were detected. An upper limit for C2H5CONH2 at centimeter wavelengths was determined to be N T < 1.8 × 1014 cm−2 and an upper limit to the C2H5CONH2/CH3CONH2 ratio is found to be <2.34. This work again questions the initial detection of C2H5CONH2 and indicates that more complex peptide-like structures may have difficulty forming in the ISM or are below the detection limits of current astronomical facilities. Additional structurally related species are provided to aid in future laboratory and astronomical searches.
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Weaver, Susanna L. Widicus, Robin T. Garrod, Jacob C. Laas y Eric Herbst. "Models of Hot Cores with Complex Molecules". Proceedings of the International Astronomical Union 7, S280 (junio de 2011): 79–87. http://dx.doi.org/10.1017/s1743921311024884.
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AbstractRecent models of hot cores have incorporated previously-uninvestigated chemical pathways that lead to the formation of complex organic molecules (COMs; i.e. species containing six or more atoms). In addition to the gas-phase ion-molecule reactions long thought to dominate the organic chemistry in these regions, these models now include photodissociation-driven grain surface reaction pathways that can also lead to COMs. Here, simple grain surface ice species photodissociate to form small radicals such as OH, CH3, CH2OH, CH3O, HCO, and NH2. These species become mobile at temperatures above 30 K during the warm-up phase of star formation. Radical-radical addition reactions on grain surfaces can then form an array of COMs that are ejected into the gas phase at higher temperatures. Photodissociation experiments on pure and mixed ices also show that these complex molecules can indeed form from simple species. The molecules predicted to form from this type of chemistry reasonably match the organic inventory observed in high mass hot cores such as Sgr B2(N) and Orion-KL. However, the relative abundances of the observed molecules differ from the predicted values, and also differ between sources. Given this disparity, it remains unclear whether grain surface chemistry governed by photodissociation is the dominant mechanism for the formation of COMs, or whether other unexplored gas-phase reaction pathways could also contribute significantly to their formation. The influence that the physical conditions of the source have on the chemical inventory also remains unclear. Here we overview the chemical pathways for COM formation in hot cores. We also present new modeling results that begin to narrow down the possible routes for production of COMs based on the observed relative abundances of methyl formate (HCOOCH3) and its C2H4O2 structural isomers.
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Abplanalp, Matthew J., Samer Gozem, Anna I. Krylov, Christopher N. Shingledecker, Eric Herbst y Ralf I. Kaiser. "A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules". Proceedings of the National Academy of Sciences 113, n.º 28 (5 de julio de 2016): 7727–32. http://dx.doi.org/10.1073/pnas.1604426113.
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Complex organic molecules such as sugars and amides are ubiquitous in star- and planet-forming regions, but their formation mechanisms have remained largely elusive until now. Here we show in a combined experimental, computational, and astrochemical modeling study that interstellar aldehydes and enols like acetaldehyde (CH3CHO) and vinyl alcohol (C2H3OH) act as key tracers of a cosmic-ray-driven nonequilibrium chemistry leading to complex organics even deep within low-temperature interstellar ices at 10 K. Our findings challenge conventional wisdom and define a hitherto poorly characterized reaction class forming complex organic molecules inside interstellar ices before their sublimation in star-forming regions such as SgrB2(N). These processes are of vital importance in initiating a chain of chemical reactions leading eventually to the molecular precursors of biorelevant molecules as planets form in their interstellar nurseries.
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Rojas-García, O. S., A. I. Gómez-Ruiz, A. Palau, M. T. Orozco-Aguilera, M. Chavez Dagostino y S. E. Kurtz. "Interstellar Complex Organic Molecules in SiO-traced Massive Outflows". Astrophysical Journal Supplement Series 262, n.º 1 (19 de agosto de 2022): 13. http://dx.doi.org/10.3847/1538-4365/ac81cb.
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Abstract The interstellar medium contains dust and gas, in which molecules can proliferate at high densities and in cold conditions. Interstellar complex organic molecules (iCOMs) are C-bearing species that contain at least six atoms. As they are detected in young stellar objects, iCOMs are expected to inhabit early stages of star formation evolution. In this study, we try to determine which iCOMs are present in the outflow component of massive protostars. To do this, we analyzed the morphological extension of blue- and redshifted iCOM emission in a sample of 11 massive protostars employing mapping observations at 1 mm within a ∼1 GHz bandwidth for both the IRAM-30 m and APEX telescopes. We modeled the iCOM emission of the central pointing spectra of our objects using the XCLASS local thermal equilibrium radiative transfer code. We detected the presence of several iCOMs such as CH3OH, 13CH3OH, CH3OCHO, C2H5C15N, and (c-C3H2)CH2. In G034.41+0.24, G327.29-0.58, G328.81+0.63, G333.13-0.43, G340.97-1.02, G351.45+0.66, and G351.77-0.54, the iCOM lines show a faint broad-line profile. Due to the offset peak positions of the blue- and redshifted emission, covering from ∼0.1 to 0.5 pc, these wings are possibly related to movements external to the compact core, such as large-scale low-velocity outflows. We have also established a correlation between the parent iCOM molecule CH3OH and the shock tracer SiO, reinforcing the hypothesis that shock environments provide the conditions to boost the formation of iCOMs via gas-phase reactions.
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Nazari, P., M. L. van Gelder, E. F. van Dishoeck, B. Tabone, M. L. R. van ’t Hoff, N. F. W. Ligterink, H. Beuther et al. "Complex organic molecules in low-mass protostars on Solar System scales". Astronomy & Astrophysics 650 (junio de 2021): A150. http://dx.doi.org/10.1051/0004-6361/202039996.
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Context. The chemical inventory of planets is determined by the physical and chemical processes that govern the early phases of star formation. Nitrogen-bearing species are of interest as many provide crucial precursors in the formation of life-related matter. Aims. The aim is to investigate nitrogen-bearing complex organic molecules towards two deeply embedded Class 0 low-mass protostars (Perseus B1-c and Serpens S68N) at millimetre wavelengths with the Atacama Large Millimeter/submillimeter Array (ALMA). Next, the results of the detected nitrogen-bearing species are compared with those of oxygen-bearing species for the same and other sources. The similarities and differences are used as further input to investigate the underlying formation pathways. Methods. ALMA observations of B1-c and S68N in Band 6 (~1 mm) and Band 5 (~2 mm) are studied at ~0.5′′ resolution, complemented by Band 3 (~3 mm) data in a ~2.5′′ beam. The spectra are analysed for nitrogen-bearing species using the CASSIS spectral analysis tool, and the column densities and excitation temperatures are determined. A toy model is developed to investigate the effect of source structure on the molecular emission. Results. Formamide (NH2CHO), ethyl cyanide (C2H5CN), isocyanic acid (HNCO, HN13CO, DNCO), and methyl cyanide (CH3CN, CH2DCN, and CHD2CN) are identified towards the investigated sources. Their abundances relative to CH3OH and HNCO are similar for the two sources, with column densities that are typically an order of magnitude lower than those of oxygen-bearing species. The largest variations, of an order of magnitude, are seen for NH2CHO abundance ratios with respect to HNCO and CH3OH and do not correlate with the protostellar luminosity. In addition, within uncertainties, the nitrogen-bearing species have similar excitation temperatures to those of oxygen-bearing species (~100–300 K). The measured excitation temperatures are larger than the sublimation temperatures for the respective species. Conclusions. The similarity of most abundances with respect to HNCO for the investigated sources, including those of CH2DCN and CHD2CN, hints at a shared chemical history, especially the high D-to-H ratio in cold regions prior to star formation. However, some of the variations in abundances may reflect the sensitivity of the chemistry to local conditions such as temperature (e.g. NH2CHO), while others may arise from differences in the emitting areas of the molecules linked to their different binding energies in the ice. The excitation temperatures likely reflect the mass-weighted kinetic temperature of a gas that follows a power law structure. The two sources discussed in this work add to the small number of sources that have been subjected to such a detailed chemical analysis on Solar System scales. Future data from the James Webb Space Telescope will allow a direct comparison between the ice and gas abundances of both smaller and larger nitrogen-bearing species.
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Cecchi-Pestellini, Cesare, Flavio Scappini, Rosalba Saija, Maria Antonia Iatì, Arianna Giusto, Santi Aiello, Ferdinando Borghese y Paolo Denti. "On the formation and survival of complex prebiotic molecules in interstellar grain aggregates". International Journal of Astrobiology 3, n.º 4 (octubre de 2004): 287–93. http://dx.doi.org/10.1017/s1473550404001971.
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The aggregation of interstellar grains as a result of ballistic collisions produces loosely packed structures with much of their internal volume composed by vacuum (cavities). The molecular material present on the surfaces of the cavities gives rise to a series of reactions induced by cosmic rays, UV radiation, thermal shocks, etc., in high reducing conditions. Thus, a terrestrial type chemistry is given the possibility to evolve inside these cavities. The resulting products are different and of a wider range than those from gas-phase or surface chemistry in molecular clouds. Under conditions similar to those in the aggregate cavities, laboratory experiments have produced amino acids, sugars and other organic compounds from simple precursors. In dense star-forming regions, the molecular species inside aggregates are efficiently shielded against the local UV field. The same molecules were incorporated in the material which formed the Earth, as well as other planets, during the process of its formation and afterwards fell on the surface via comets, meteorites, interstellar dust, etc. This was the source material that can produce, under favorable circumstances, the biopolymers needed for life. The astronomical observations of organic molecules in star-forming regions and the results of analyses of meteorites and cometary dust seem to support the present hypothesis that complex prebiotic molecules form inside dust aggregates and therein survive the journey to planetary systems. The Miller experiment is revisited through innumerable repetitions inside dust grain aggregates.
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Mifsud, Duncan V., Péter Herczku, Béla Sulik, Zoltán Juhász, István Vajda, István Rajta, Sergio Ioppolo, Nigel J. Mason, Giovanni Strazzulla y Zuzana Kaňuchová. "Proton and Electron Irradiations of CH4:H2O Mixed Ices". Atoms 11, n.º 2 (22 de enero de 2023): 19. http://dx.doi.org/10.3390/atoms11020019.
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The organic chemistry occurring in interstellar environments may lead to the production of complex molecules that are relevant to the emergence of life. Therefore, in order to understand the origins of life itself, it is necessary to probe the chemistry of carbon-bearing molecules under conditions that simulate interstellar space. Several of these regions, such as dense molecular cores, are exposed to ionizing radiation in the form of galactic cosmic rays, which may act as an important driver of molecular destruction and synthesis. In this paper, we report the results of a comparative and systematic study of the irradiation of CH4:H2O ice mixtures by 1 MeV protons and 2 keV electrons at 20 K. We demonstrate that our irradiations result in the formation of a number of new products, including both simple and complex daughter molecules such as C2H6, C3H8, C2H2, CH3OH, CO, CO2, and probably also H2CO. A comparison of the different irradiation regimes has also revealed that proton irradiation resulted in a greater abundance of radiolytic daughter molecules compared to electron irradiation, despite a lower radiation dose having been administered. These results are important in the context of the radiation astrochemistry occurring within the molecular cores of dense interstellar clouds, as well as on outer Solar System objects.
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Zahorecz, Sarolta, Izaskun Jimenez-Serra, Leonardo Testi, Katharina Immer, Francesco Fontani, Paola Caselli, L. Viktor Toth, Ke Wang y Toshikazu Onishi. "Deuteration of formaldehyde - an important precursor of hydrogenated complex organic molecules - during star formation in our Galaxy". Proceedings of the International Astronomical Union 14, S345 (agosto de 2018): 337–38. http://dx.doi.org/10.1017/s1743921319001765.
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AbstractFormaldehyde (H2CO) and its deuterated forms can be produced both in the gas phase and on grain surfaces. However, the relative importance of these two chemical pathways is unclear. Our recent single dish observation of formaldehyde and its deuterated species suggests that they form mostly on grain surfaces although some gas-phase contribution is expected at the warm HMPO stage. Since the single dish beam is larger, and since these high-mass star-forming regions are clustered and complex, it is however unclear whether the emission arises from the protostellar sources or from starless/pre-stellar cores associated with them. Therefore, interferometric observations are needed to separate the emission originating from the small and dense cores, to disentangle their formation routes and then being able to use them as powerful diagnostic tools of the physical and chemical properties of high-mass star forming regions.
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Haupa, Karolina Anna, Wei-Siong Ong y Yuan-Pern Lee. "Hydrogen abstraction in astrochemistry: formation of ˙CH2CONH2 in the reaction of H atom with acetamide (CH3CONH2) and photolysis of ˙CH2CONH2 to form ketene (CH2CO) in solid para-hydrogen". Physical Chemistry Chemical Physics 22, n.º 11 (2020): 6192–201. http://dx.doi.org/10.1039/c9cp06279c.
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The amide bond of acetamide is unaffected by hydrogen exposure, but the hydrogen abstraction on its methyl site activates this molecule to react with other species to extend its size as a first step to form interstellar complex organic molecules.
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Ehrenfreund, Pascale, Marco Spaans y Nils G. Holm. "The evolution of organic matter in space". Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 369, n.º 1936 (13 de febrero de 2011): 538–54. http://dx.doi.org/10.1098/rsta.2010.0231.
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Carbon, and molecules made from it, have already been observed in the early Universe. During cosmic time, many galaxies undergo intense periods of star formation, during which heavy elements like carbon, oxygen, nitrogen, silicon and iron are produced. Also, many complex molecules, from carbon monoxide to polycyclic aromatic hydrocarbons, are detected in these systems, like they are for our own Galaxy. Interstellar molecular clouds and circumstellar envelopes are factories of complex molecular synthesis. A surprisingly high number of molecules that are used in contemporary biochemistry on the Earth are found in the interstellar medium, planetary atmospheres and surfaces, comets, asteroids and meteorites and interplanetary dust particles. Large quantities of extra-terrestrial material were delivered via comets and asteroids to young planetary surfaces during the heavy bombardment phase. Monitoring the formation and evolution of organic matter in space is crucial in order to determine the prebiotic reservoirs available to the early Earth. It is equally important to reveal abiotic routes to prebiotic molecules in the Earth environments. Materials from both carbon sources (extra-terrestrial and endogenous) may have contributed to biochemical pathways on the Earth leading to life’s origin. The research avenues discussed also guide us to extend our knowledge to other habitable worlds.
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Aikawa, Yuri y Kenji Furuya. "Gas-dust chemistry of volatiles in the star and planetary system formation". Proceedings of the International Astronomical Union 15, S350 (abril de 2019): 161–68. http://dx.doi.org/10.1017/s1743921319008263.
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AbstractThe focus of this work is on two topics: (i) formation of complex organic molecules (COMs) and (ii) isotope fractionation. Various COMs, which are C, H-containing molecules consisting of 6 atoms and more, have been detected in the central warm region of protostellar cores. Most of this review is about gas-grain chemical models, which have been constructed to evaluate the mechanisms and efficiency of the COM formation. The relevant physical and chemical processes are investigated in laboratory experiments, as reported in other articles in this volume.The isotope fractionation of volatile elements is observed in both the interstellar medium (ISM) and Solar system material. While exothermic exchange reactions enrich molecules with heavier isotopes such as Deuterium, the isotope selective photodissociation can be coupled with ice formation to enrich the ice mantle with rare isotopes. The efficiency of this fractionation depends on the photodesorption yields, which has been studied in laboratory experiments.
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Inostroza-Pino, Natalia, Diego Mardones, Jixing J. X. Ge y Desmond MacLeod-Carey. "Formation pathways of complex organic molecules: OH• projectile colliding with methanol ice mantle (CH3OH)10". Astronomy & Astrophysics 641 (septiembre de 2020): A14. http://dx.doi.org/10.1051/0004-6361/202037904.
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In this article, we simulated the collisions of an OH• projectile impacting on a methanol cluster formed by ten units of methanol to mimic an ice mantle (CH3OH)10. The chemical processes occurring after the impact were studied through Born-Oppenheimer (ab-initio) molecular dynamics. We focus on collisions with initial kinetic impact energy of 10–22 eV, where the richest chemistry happens. We report the formation mechanisms of stable complex organic molecules (COMs) such as methoxymethanol CH3OCH2OH, formic acid HCOOH, formyl radical HCO, formaldehyde H2CO and its elusive HCOH isomer. We show that CH2(OH)2, •CH2OH or +CH2OH are key intermediates to generate H2CO and other COMs. We compare the outcomes using OH• with those using OH− projectiles. These processes are likely relevant to the production of COMs in astrophysical environments. We discuss its formation mechanism and the astrophysical implications of these chemical pathways in star-forming regions.
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Jørgensen, J. K., H. S. P. Müller, H. Calcutt, A. Coutens, M. N. Drozdovskaya, K. I. Öberg, M. V. Persson, V. Taquet, E. F. van Dishoeck y S. F. Wampfler. "The ALMA-PILS survey: isotopic composition of oxygen-containing complex organic molecules toward IRAS 16293–2422B". Astronomy & Astrophysics 620 (diciembre de 2018): A170. http://dx.doi.org/10.1051/0004-6361/201731667.
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Context. One of the important questions of astrochemistry is how complex organic molecules, including potential prebiotic species, are formed in the envelopes around embedded protostars. The abundances of minor isotopologues of a molecule, in particular the D- and 13C-bearing variants, are sensitive to the densities, temperatures and timescales characteristic of the environment in which they form, and can therefore provide important constraints on the formation routes and conditions of individual species. Aims. The aim of this paper is to systematically survey the deuteration and the 13C content of a variety of oxygen-bearing complex organic molecules on solar system scales toward the “B component” of the protostellar binary IRAS16293–2422. Methods. We have used the data from an unbiased molecular line survey of the protostellar binary IRAS16293−2422 between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The data probe scales of 60 AU (diameter) where most of the organic molecules are expected to have sublimated off dust grains and be present in the gas phase. The deuterated and 13C isotopic species of ketene, acetaldehyde and formic acid, as well as deuterated ethanol, are detected unambiguously for the first time in the interstellar medium. These species are analysed together with the 13C isotopic species of ethanol, dimethyl ether and methyl formate along with mono-deuterated methanol, dimethyl ether and methyl formate. Results. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of ≈2% and the other, the more complex species, D/H ratios of 4–8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short timescale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 and 300 K. This likely reflects the binding energies of the individual species, in good agreement with what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. Tentative identifications suggest that the same may apply for 13C isotopologues of methyl formate and ethanol. If confirmed, this may be a clue to their formation at the late prestellar or early protostellar phases with an enhancement of the available 13C relative to 12C related to small differences in binding energies for CO isotopologues or the impact of FUV irradiation by the central protostar. Conclusions. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species.
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Calcutt, H., J. K. Jørgensen, H. S. P. Müller, L. E. Kristensen, A. Coutens, T. L. Bourke, R. T. Garrod et al. "The ALMA-PILS survey: complex nitriles towards IRAS 16293–2422". Astronomy & Astrophysics 616 (agosto de 2018): A90. http://dx.doi.org/10.1051/0004-6361/201732289.
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Context. Complex organic molecules are readily detected in the inner regions of the gaseous envelopes of forming protostars. Their detection is crucial to understanding the chemical evolution of the Universe and exploring the link between the early stages of star formation and the formation of solar system bodies, where complex organic molecules have been found in abundance. In particular, molecules that contain nitrogen are interesting due to the role nitrogen plays in the development of life and the compact scales such molecules have been found to trace around forming protostars. Aims. The goal of this work is to determine the inventory of one family of nitrogen-bearing organic molecules, complex nitriles (molecules with a –C≡N functional group) towards two hot corino sources in the low-mass protostellar binary IRAS 16293–2422. This work explores the abundance differences between the two sources, the isotopic ratios, and the spatial extent derived from molecules containing the nitrile functional group. Methods. Using data from the Protostellar Interferometric Line Survey (PILS) obtained with ALMA, we determine abundances and excitation temperatures for the detected nitriles. We also present a new method for determining the spatial structure of sources with high line density and large velocity gradients – Velocity-corrected INtegrated emission (VINE) maps. Results. We detect methyl cyanide (CH3CN) as well as five of its isotopologues, including CHD2CN, which is the first detection in the interstellar medium (ISM). We also detect ethyl cyanide (C2H5CN), vinyl cyanide (C2H3CN), and cyanoacetylene (HC3N). We find that abundances are similar between IRAS 16293A and IRAS 16293B on small scales except for vinyl cyanide which is only detected towards the latter source. This suggests an important difference between the sources either in their evolutionary stage or warm-up timescales. We also detect a spatially double-peaked emission for the first time in molecular emission in the A source, suggesting that this source is showing structure related to a rotating toroid of material. Conclusions. With high-resolution observations, we have been able to show for the first time a number of important similarities and differences in the nitrile chemistry in these objects. These illustrate the utility of nitriles as potential tracers of the physical conditions in star-forming regions.
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Rawlings, J. M. C., D. A. Williams, S. Viti, C. Cecchi-Pestellini y W. W. Duley. "The formation of glycine and other complex organic molecules in exploding ice mantles". Faraday Discuss. 168 (2014): 369–88. http://dx.doi.org/10.1039/c3fd00155e.
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Complex Organic Molecules (COMs), such as propylene (CH3CHCH2) and the isomers of C2H4O2 are detected in cold molecular clouds (such as TMC-1) with high fractional abundances (Marcelino et al., Astrophys. J., 2007, 665, L127). The formation mechanism for these species is the subject of intense speculation, as is the possibility of the formation of simple amino acids such as glycine (NH2CH2COOH). At typical dark cloud densities, normal interstellar gas-phase chemistries are inefficient, whilst surface chemistry is at best ill defined and does not easily reproduce the abundance ratios observed in the gas phase. Whatever mechanism(s) is/are operating, it/they must be both efficient at converting a significant fraction of the available carbon budget into COMs, and capable of efficiently returning the COMs to the gas phase. In our previous studies we proposed a complementary, alternative mechanism, in which medium- and large-sized molecules are formed by three-body gas kinetic reactions in the warm high density gas phase. This environment exists, for a very short period of time, after the total sublimation of grain ice mantles in transient co-desorption events. In order to drive the process, rapid and efficient mantle sublimation is required and we have proposed that ice mantle ‘explosions’ can be driven by the catastrophic recombination of trapped hydrogen atoms, and other radicals, in the ice. Repeated cycles of freeze-out and explosion can thus lead to a cumulative molecular enrichment of the interstellar medium. Using existing studies we based our chemical network on simple radical addition, subject to enthalpy and valency restrictions. In this work we have extended the chemistry to include the formation pathways of glycine and other large molecular species that are detected in molecular clouds. We find that the mechanism is capable of explaining the observed molecular abundances and complexity in these sources. We find that the proposed mechanism is easily capable of explaining the large abundances of all three isomers of C2H4O2 that are observationally inferred for star-forming regions. However, the model currently does not provide an obvious explanation for the predominance of methyl formate, suggesting that some refinement to our (very simplistic) chemistry is necessary. The model also predicts the production of glycine at a (lower) abundance level, that is consistent with its marginal detection in astrophysical sources.
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Baek, Giseon, Jeong-Eun Lee, Tomoya Hirota, Kee-Tae Kim y Mi Kyoung Kim. "Complex Organic Molecules Detected in 12 High-mass Star-forming Regions with Atacama Large Millimeter/submillimeter Array". Astrophysical Journal 939, n.º 2 (1 de noviembre de 2022): 84. http://dx.doi.org/10.3847/1538-4357/ac81d3.
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Abstract Recent astrochemical models and experiments have explained that complex organic molecules (COMs; molecules composed of six or more atoms) are produced on the dust grain mantles in cold and dense gas in prestellar cores. However, the detailed chemical processes and the roles of physical conditions on chemistry are still far from understood. To address these questions, we investigated 12 high-mass star-forming regions using Atacama Large Millimeter/submillimeter Array (ALMA) Band 6 observations. They are associated with 44/95 GHz class I and 6.7 GHz class II CH3OH masers, indicative of undergoing active accretion. We found 28 hot cores with COM emission among 68 continuum peaks at 1.3 mm and specified 10 hot cores associated with 6.7 GHz class II CH3OH masers. Up to 19 COMs are identified including oxygen- and nitrogen-bearing molecules and their isotopologues in cores. The derived abundances show a good agreement with those from other low- and high-mass star-forming regions, implying that the COM chemistry is predominantly set by the ice chemistry in the prestellar core stage. One clear trend is that the COM detection rate steeply grows with the gas column density, which can be attributed to the efficient formation of COMs in dense cores. In addition, cores associated with a 6.7 GHz class II CH3OH maser tend to be enriched with COMs. Finally, our results suggest that the enhanced abundances of several molecules in our hot cores could be originated by the active accretion as well as different physical conditions of cores.
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Pagani, L., E. Bergin, P. F. Goldsmith, G. Melnick, R. Snell y C. Favre. "The complexity of Orion: an ALMA view". Astronomy & Astrophysics 624 (abril de 2019): L5. http://dx.doi.org/10.1051/0004-6361/201935267.
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The chemistry of complex organic molecules in interstellar dark clouds is still highly uncertain in part because of the lack of constraining observations. Orion is the closest massive star-forming region, and observations making use of ALMA allow us to separate the emission regions of various complex organic molecules (COMs) in both velocity and space. Orion also benefits from an exceptional situation, in that it is the site of a powerful explosive event that occurred ∼550 years ago. We show that the closely surrounding Kleinmann-Low region has clearly been influenced by this explosion; some molecular species have been pushed away from the densest parts while others have remained in close proximity. This dynamical segregation reveals the time dependence of the chemistry and, therefore allows us to better constrain the formation sequence of COMs and other species, including deuterated molecules.
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Linnartz, Harold, Jean-Baptiste Bossa, Jordy Bouwman, Herma M. Cuppen, Steven H. Cuylle, Ewine F. van Dishoeck, Edith C. Fayolle et al. "Solid State Pathways towards Molecular Complexity in Space". Proceedings of the International Astronomical Union 7, S280 (junio de 2011): 390–404. http://dx.doi.org/10.1017/s1743921311025142.
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AbstractIt has been a long standing problem in astrochemistry to explain how molecules can form in a highly dilute environment such as the interstellar medium. In the last decennium more and more evidence has been found that the observed mix of small and complex, stable and highly transient species in space is the cumulative result of gas phase and solid state reactions as well as gas-grain interactions. Solid state reactions on icy dust grains are specifically found to play an important role in the formation of the more complex “organic” compounds. In order to investigate the underlying physical and chemical processes detailed laboratory based experiments are needed that simulate surface reactions triggered by processes as different as thermal heating, photon (UV) irradiation and particle (atom, cosmic ray, electron) bombardment of interstellar ice analogues. Here, some of the latest research performed in the Sackler Laboratory for Astrophysics in Leiden, the Netherlands is reviewed. The focus is on hydrogenation, i.e., H-atom addition reactions and vacuum ultraviolet irradiation of interstellar ice analogues at astronomically relevant temperatures. It is shown that solid state processes are crucial in the chemical evolution of the interstellar medium, providing pathways towards molecular complexity in space.
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Layssac, Y., A. Gutiérrez-Quintanilla, T. Chiavassa y F. Duvernay. "Detection of glyceraldehyde and glycerol in VUV processed interstellar ice analogues containing formaldehyde: a general formation route for sugars and polyols". Monthly Notices of the Royal Astronomical Society 496, n.º 4 (2 de julio de 2020): 5292–307. http://dx.doi.org/10.1093/mnras/staa1875.
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ABSTRACT Complex organic molecules (COMs) have been identified toward high- and low-mass protostars as well as molecular clouds. Among them, sugar-like and polyol two carbon-bearing molecules such as glycolaldehyde (GA) and ethylene glycol (EG) are of special interest. Recent laboratory experiments have shown that they can efficiently be formed via atom addition reactions between accreting H-atoms and CO molecules or via energetic processes (UV, electrons) on ice analogues containing methanol or formaldehyde. In this study, we report new laboratory experiments on the low-temperature solid state formation of complex organic molecules – the first sugar glyceraldehyde and its saturated derivative glycerol – through VUV photolysis performed at three different temperatures (15, 50, and 90 K) of astrochemically relevant ices composed of water and formaldehyde. We get evidence that the species production depends on the ice temperature during photolysis. The results presented here indicate that a general scheme of aldose and polyol formation is plausible and that heavier COMs than GA and EG could exist in interstellar environments. We propose a general pathway involving radical-formaldehyde reactions as common initiation step for aldose and polyol formation. Future telescope observations may give additional clues on their presence in star-forming regions as observations are currently limited because of the detection thresholds.
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Fedoseev, Gleb, Danna Qasim, Ko-Ju Chuang, Sergio Ioppolo, Thanja Lamberts, Ewine F. van Dishoeck y Harold Linnartz. "Hydrogenation of Accreting C Atoms and CO Molecules–Simulating Ketene and Acetaldehyde Formation Under Dark and Translucent Cloud Conditions". Astrophysical Journal 924, n.º 2 (1 de enero de 2022): 110. http://dx.doi.org/10.3847/1538-4357/ac3834.
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Abstract Simple and complex organic molecules (COMs) are observed along different phases of star and planet formation and have been successfully identified in prestellar environments such as dark and translucent clouds. Yet the picture of organic molecule formation at those earliest stages of star formation is not complete and an important reason is the lack of specific laboratory experiments that simulate carbon atom addition reactions on icy surfaces of interstellar grains. Here we present experiments in which CO molecules as well as C and H atoms are codeposited with H2O molecules on a 10 K surface mimicking the ongoing formation of an “H2O-rich” ice mantle. To simulate the effect of impacting C atoms and resulting surface reactions with ice components, a specialized C-atom beam source is used, implemented on SURFRESIDE3, an ultra-high vacuum cryogenic setup. Formation of ketene (CH2CO) in the solid state is observed in situ by means of reflection absorption IR spectroscopy. C18O and D isotope labeled experiments are performed to further validate the formation of ketene. Data analysis supports that CH2CO is formed through C-atom addition to a CO molecule, followed by successive hydrogenation transferring the formed :CCO into ketene. Efficient formation of ketene is in line with the absence of an activation barrier in C+CO reaction reported in the literature. We also discuss and provide experimental evidence for the formation of acetaldehyde (CH3CHO) and possible formation of ethanol (CH3CH2OH), two COM derivatives of CH2CO hydrogenation. The underlying reaction network is presented and the astrochemical implications of the derived pathways are discussed.
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Walsh, Catherine, Eric Herbst, Hideko Nomura, T. J. Millar y Susanna Widicus Weaver. "Complex organic molecules along the accretion flow in isolated and externally irradiated protoplanetary disks". Faraday Discuss. 168 (2014): 389–421. http://dx.doi.org/10.1039/c3fd00135k.
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The birth environment of the Sun will have influenced the physical and chemical structure of the pre-solar nebula, including the attainable chemical complexity reached in the disk, important for prebiotic chemistry. The formation and distribution of complex organic molecules (COMs) in a disk around a T Tauri star is investigated for two scenarios: (i) an isolated disk, and (ii) a disk irradiated externally by a nearby massive star. The chemistry is calculated along the accretion flow from the outer disk inwards using a comprehensive network which includes gas-phase reactions, gas-grain interactions, and thermal grain-surface chemistry. Two simulations are performed, one beginning with complex ices and one with simple ices only. For the isolated disk, COMs are transported without major chemical alteration into the inner disk where they thermally desorb into the gas reaching an abundance representative of the initial assumed ice abundance. For simple ices, COMs can efficiently form on grain surfaces under the conditions in the outer disk. Gas-phase COMs are released into the molecular layer via photodesorption. For the irradiated disk, complex ices are also transported inwards; however, they undergo thermal processing caused by the warmer conditions in the irradiated disk which tends to reduce their abundance along the accretion flow. For simple ices, grain-surface chemistry cannot efficiently synthesise COMs in the outer disk because the necessary grain-surface radicals, which tend to be particularly volatile, are not sufficiently abundant on the grain surfaces. Gas-phase COMs are formed in the inner region of the irradiated disk via gas-phase chemistry induced by the desorption of strongly bound molecules such as methanol; hence, the abundances are not representative of the initial molecular abundances injected into the outer disk. These results suggest that the composition of comets formed in isolated disks may differ from those formed in externally irradiated disks with the latter composed of more simple ices.
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Enrique-Romero, Joan, Albert Rimola, Cecilia Ceccarelli, Piero Ugliengo, Nadia Balucani y Dimitrios Skouteris. "Quantum Mechanical Simulations of the Radical–Radical Chemistry on Icy Surfaces". Astrophysical Journal Supplement Series 259, n.º 2 (22 de marzo de 2022): 39. http://dx.doi.org/10.3847/1538-4365/ac480e.
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Abstract The formation of the interstellar complex organic molecules (iCOMs) is a hot topic in astrochemistry. One of the main paradigms trying to reproduce the observations postulates that iCOMs are formed on the ice mantles covering the interstellar dust grains as a result of radical–radical coupling reactions. We investigate iCOM formation on the icy surfaces by means of computational quantum mechanical methods. In particular, we study the coupling and direct hydrogen abstraction reactions involving the CH3 + X systems (X = NH2, CH3, HCO, CH3O, CH2OH) and HCO + Y (Y = HCO, CH3O, CH2OH), plus the CH2OH + CH2OH and CH3O + CH3O systems. We computed the activation energy barriers of these reactions, as well as the binding energies of all the studied radicals, by means of density functional theory calculations on two ice water models, made of 33 and 18 water molecules. Then, we estimated the efficiency of each reaction using the reaction activation, desorption, and diffusion energies and derived kinetics with the Eyring equations. We find that radical–radical chemistry on surfaces is not as straightforward as usually assumed. In some cases, direct H-abstraction reactions can compete with radical–radical couplings, while in others they may contain large activation energies. Specifically, we found that (i) ethane, methylamine, and ethylene glycol are the only possible products of the relevant radical–radical reactions; (ii) glyoxal, methyl formate, glycolaldehyde, formamide, dimethyl ether, and ethanol formation is likely in competition with the respective H-abstraction products; and (iii) acetaldehyde and dimethyl peroxide do not seem to be likely grain-surface products.
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Whittet, D. C. B. "Interstellar Dust and the Organic Inventories of Early Solar Systems". Symposium - International Astronomical Union 213 (2004): 163–68. http://dx.doi.org/10.1017/s0074180900193192.
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Interstellar dust grains are vectors for cosmic carbon and other biogenic chemical elements. They deliver carbon to protoplanetary disks in various refractory phases (amorphous, graphitic, etc.), and they are coated with icy mantles that contain organic molecules and water. The nature of the organics present in and on the dust appears to be closely related to physical conditions. Complex molecules may be synthesized when simple ices are irradiated. Astronomical observations show that this occurs in the vicinity of certain massive protostars, but it is not known whether our Solar System formed in such a region. Organic matter does not survive cycling though diffuse regions of interstellar space; any organics delivered to the early Earth must have originated in the parent molecular cloud, or in the solar nebula itself. A key question is thus identified: What was the star-formation environment of the Solar System? Possible constraints are briefly discussed.
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Kiskin, Mikhail Yu, Anton I. Vasyunin y Vitaly V. Akimkin. "A numerical approach to model chemistry of complex organic molecules in a protoplanetary disk". Open Astronomy 31, n.º 1 (1 de enero de 2022): 80–91. http://dx.doi.org/10.1515/astro-2022-0009.
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Abstract Multiphase astrochemical modeling presents a numerical challenge especially for the simulation of objects with the wide range of physical parameters such as protoplanetary disks. We demonstrate an implementation of the analytical Jacobian for the numerical integration of the system of differential rate equations that govern chemical evolution in star-forming regions. The analytical Jacobian allowed us to greatly improve the stability of the code in protoplanetary disk conditions. We utilize the MONACO code to study the evolution of abundances of chemical species in protoplanetary disks. The chemical model includes 670 species and 6,015 reactions in the gas phase and on interstellar grains. The specific feature of the utilized chemical model is the inclusion of low-temperature chemical processes leading to the formation of complex organic molecules (COMs), included previously in the models of chemistry of COMs in prestellar clouds. To test the impact of analytical Jacobian on the stability of numerical simulations of chemical evolution in protoplanetary disks, we calculated the chemical composition of the disk using a two-phase model and four variants of the chemical reaction network, three values of the surface diffusion rates, and two types of the initial chemical composition. We also show a preliminary implementation of the analytical Jacobian to a three-phase model.
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Brunken, Nashanty G. C., Alice S. Booth, Margot Leemker, Pooneh Nazari, Nienke van der Marel y Ewine F. van Dishoeck. "A major asymmetric ice trap in a planet-forming disk". Astronomy & Astrophysics 659 (marzo de 2022): A29. http://dx.doi.org/10.1051/0004-6361/202142981.
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The complex organic molecules (COMs) detected in star-forming regions are the precursors of the prebiotic molecules that can lead to the emergence of life. By studying COMs in more evolved protoplanetary disks we can gain a better understanding of how they are incorporated into planets. This paper presents ALMA band 7 observations of the dust and ice trap in the protoplanetary disk around Oph IRS 48. We report the first detection of dimethyl ether (CH3OCH3) in a planet-forming disk and a tentative detection of methyl formate (CH3OCHO). We determined column densities for the detected molecules and upper limits on non-detected species using the CASSIS spectral analysis tool. The inferred column densities of CH3OCH3 and CH3OCHO with respect to methanol (CH3OH) are of order unity, indicating unusually high abundances of these species compared to other environments. Alternatively, the 12CH3OH emission is optically thick and beam diluted, implying a higher CH3OH column density and a smaller emitting area than originally thought. The presence of these complex molecules can be explained by thermal ice sublimation, where the dust cavity edge is heated by irradiation and the full volatile ice content is observable in the gas phase. This work confirms the presence of oxygen-bearing molecules more complex than CH3OH in protoplanetary disks for the first time. It also shows that it is indeed possible to trace the full interstellar journey of COMs across the different evolutionary stages of star, disk, and planet formation.
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Visser, Ruud, Ewine F. van Dishoeck y Steven D. Doty. "Chemical History of Molecules in Circumstellar Disks". Proceedings of the International Astronomical Union 7, S280 (junio de 2011): 138–48. http://dx.doi.org/10.1017/s1743921311024938.
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AbstractThe chemical composition of a protoplanetary disk is determined not only by in situ chemical processes during the disk phase, but also by the history of the gas and dust before it accreted from the natal envelope. In order to understand the disk's chemical composition at the time of planet formation, especially in the midplane, one has to go back in time and retrace the chemistry to the molecular cloud that collapsed to form the disk and the central star. Here we present a new astrochemical model that aims to do just that. The model follows the core collapse and disk formation in two dimensions, which turns out to be a critical upgrade over older collapse models. We predict chemical stratification in the disk due to different physical conditions encountered along different streamlines. We argue that the disk-envelope accretion shock does not play a significant role for the material in the disk at the end of the collapse phase. Finally, our model suggests that complex organic species are formed on the grain surfaces at temperatures of 20 to 40 K, rather than in the gas phase in the T > 100 K hot corino.
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Peng, Yaping, Tie Liu, Sheng-Li Qin, Tapas Baug, Hong-Li Liu, Ke Wang, Guido Garay et al. "ATOMS: ALMA Three-millimeter Observations of Massive Star-forming regions – X. Chemical differentiation among the massive cores in G9.62+0.19". Monthly Notices of the Royal Astronomical Society 512, n.º 3 (9 de marzo de 2022): 4419–40. http://dx.doi.org/10.1093/mnras/stac624.
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ABSTRACT Investigating the physical and chemical structure of massive star-forming regions is critical for understanding the formation and early evolution of massive stars. We performed a detailed line survey toward six dense cores, named MM1, MM4, MM6, MM7, MM8, and MM11, in the G9.62+0.19 star-forming region resolved in Atacama Large Millimeter/submillimeter Array (ALMA) band 3 observations. Toward these cores, about 172 transitions have been identified and attributed to 16 species, including organic oxygen-, nitrogen-, and sulphur-bearing molecules and their isotopologues. Four dense cores, MM7, MM8, MM4, and MM11, are line-rich sources. Modelling of these spectral lines reveals that the rotational temperature lies in the range 72–115, 100–163, 102–204, and 84–123 K for MM7, MM8, MM4, and MM11, respectively. The molecular column densities are 1.6 × 1015–9.2 × 1017 cm−2 toward the four cores. The cores MM8 and MM4 show a chemical difference between oxygen- and nitrogen-bearing species, i.e. MM4 is rich in oxygen-bearing molecules, while nitrogen-bearing molecules, especially vibrationally excited HC3N lines, are mainly observed in MM8. The distinct initial temperatures at the accretion phase may lead to this N/O differentiation. Through analysing column densities and spatial distributions of O-bearing complex organic molecules (COMs), we found that C2H5OH and CH3OCH3 might have a common precursor, CH3OH. CH3OCHO and CH3OCH3 are likely chemically linked. In addition, the observed variation in HC3N and HC5N emission may indicate their different formation mechanisms in hot and cold regions.
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Taquet, V., E. Bianchi, C. Codella, M. V. Persson, C. Ceccarelli, S. Cabrit, J. K. Jørgensen, C. Kahane, A. López-Sepulcre y R. Neri. "Interferometric observations of warm deuterated methanol in the inner regions of low-mass protostars". Astronomy & Astrophysics 632 (22 de noviembre de 2019): A19. http://dx.doi.org/10.1051/0004-6361/201936044.
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Methanol is a key species in astrochemistry because it is the most abundant organic molecule in the interstellar medium and is thought to be the mother molecule of many complex organic species. Estimating the deuteration of methanol around young protostars is of crucial importance because it highly depends on its formation mechanisms and the physical conditions during its moment of formation. We analyse several dozen transitions from deuterated methanol isotopologues coming from various existing observational datasets obtained with the IRAM-PdBI and ALMA sub-millimeter interferometers to estimate the methanol deuteration surrounding three low-mass protostars on Solar System scales. A population diagram analysis allows us to derive a [CH2DOH]/[CH3OH] abundance ratio of 3–6% and a [CH3OD]/[CH3OH] ratio of 0.4–1.6% in the warm inner (≤100–200 AU) protostellar regions. These values are typically ten times lower than those derived with previous single-dish observations towards these sources, but they are one to two orders of magnitude higher than the methanol deuteration measured in massive hot cores. Dust temperature maps obtained from Herschel and Planck observations show that massive hot cores are located in warmer molecular clouds than low-mass sources, with temperature differences of ~10 K. The comparison of our measured values with the predictions of the gas-grain astrochemical model GRAINOBLE shows that such a temperature difference is sufficient to explain the different deuteration observed in low- to high-mass sources. This suggests that the physical conditions of the molecular cloud at the origin of the protostars mostly govern the present-day observed deuteration of methanol and therefore of more complex organic molecules. Finally, the methanol deuteration measured towards young solar-type protostars on Solar System scales seems to be higher by a factor of ~5 than the upper limit in methanol deuteration estimated in comet Hale-Bopp. If this result is confirmed by subsequent observations of other comets, it would imply that an important reprocessing of the organic material likely occurred in the solar nebula during the formation of the Solar System.
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Manigand, S., H. Calcutt, J. K. Jørgensen, V. Taquet, H. S. P. Müller, A. Coutens, S. F. Wampfler et al. "The ALMA-PILS survey: the first detection of doubly deuterated methyl formate (CHD2OCHO) in the ISM". Astronomy & Astrophysics 623 (marzo de 2019): A69. http://dx.doi.org/10.1051/0004-6361/201832844.
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Studies of deuterated isotopologues of complex organic molecules can provide important constraints on their origin in star formation regions. In particular, the abundances of deuterated species are very sensitive to the physical conditions in the environment where they form. Because the temperatures in star formation regions are low, these isotopologues are enhanced to significant levels, which enables the detection of multiply deuterated species. However, for complex organic species, so far only the multiply deuterated variants of methanol and methyl cyanide have been reported. The aim of this paper is to initiate the characterisation of multiply deuterated variants of complex organic species with the first detection of doubly deuterated methyl formate, CHD2OCHO. We use ALMA observations from the Protostellar Interferometric Line Survey (PILS) of the protostellar binary IRAS 16293–2422 in the spectral range of 329.1 GHz to 362.9 GHz. Spectra towards each of the two protostars are extracted and analysed using a local thermal equilibrium model in order to derive the abundances of methyl formate and its deuterated variants. We report the first detection of doubly deuterated methyl formate CHD2OCHO in the ISM. The D-to-H ratio (D/H ratio) of CHD2OCHO is found to be 2–3 times higher than the D/H ratio of CH2DOCHO for both sources, similar to the results for formaldehyde from the same dataset. The observations are compared to a gas-grain chemical network coupled to a dynamical physical model, tracing the evolution of a molecular cloud until the end of the Class 0 protostellar stage. The overall D/H ratio enhancements found in the observations are of about the same magnitude as the predictions from the model for the early stages of Class 0 protostars. However, that the D/H ratio of CHD2OCHO is higher than that of CH2DOCHO is still not predicted by the model. This suggests that a mechanism enhances the D/H ratio of singly and doubly deuterated methyl formate that is not in the model, for instance, mechanisms for H–D substitutions. This new detection provides an important constraint on the formation routes of methyl formate and outlines a path forward in terms of using these ratios to determine the formation of organic molecules through observations of differently deuterated isotopologues towards embedded protostars.
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Inostroza-Pino, Natalia, Desmond MacLeod-Carey, Cristopher Heyser, Diego Mardones, Carlos Espinoza y Jixing Ge. "Formation of formaldehyde through methanol-ice-mantle (CH3OH)10 bombardment by OH+ cation". Astronomy & Astrophysics 650 (junio de 2021): A169. http://dx.doi.org/10.1051/0004-6361/202140443.
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Context. Formaldehyde H2CO was the first organic polyatomic molecule discovered in the interstellar medium to have been detected in a variety of sources. However, pathways to synthesize this molecule under interstellar conditions have yet to be discussed. Aims. We carried out a systematic study to analyze the chemical processes that can explain the H2CO formation mechanism toward a decamer of methanol (CH3OH)10 as target material to mimic an ice mantle bombarded by an OH+ cation. Methods. We performed Born-Oppenheimer (ab initio) molecular dynamics simulations to obtain the formation mechanisms of complex organic molecules (COMs) such as formaldehyde H2CO and its HCOH isomer. Results. We found that CH2OH+ and CH2(OH)2 are the main precursors to form H2CO and HCOH. We discuss its formation mechanisms and the astrophysical implications in star-forming regions. These processes are likely relevant to the production of COMs.
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Chuang, K. J., G. Fedoseev, C. Scirè, G. A. Baratta, C. Jäger, Th Henning, H. Linnartz y M. E. Palumbo. "Formation of complex organic molecules in molecular clouds: acetaldehyde, vinyl alcohol, ketene, and ethanol via the “energetic” processing of C2H2 ice". Astronomy & Astrophysics 650 (junio de 2021): A85. http://dx.doi.org/10.1051/0004-6361/202140780.
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Context. The simultaneous detection of organic molecules of the form C2HnO, such as ketene (CH2CO), acetaldehyde (CH3CHO), and ethanol (CH3CH2OH), toward early star-forming regions offers hints of a shared chemical history. Several reaction routes have been proposed and experimentally verified under various interstellar conditions to explain the formation pathways involved. Most noticeably, the non-energetic processing of C2H2 ice with OH-radicals and H-atoms was shown to provide formation routes to ketene, acetaldehyde, ethanol, and vinyl alcohol (CH2CHOH) along the H2O formation sequence on grain surfaces in translucent clouds. Aims. In this work, the non-energetic formation scheme is extended with laboratory measurements focusing on the energetic counterpart, induced by cosmic rays penetrating the H2O-rich ice mantle. The focus here is on the H+ radiolysis of interstellar C2H2:H2O ice analogs at 17 K. Methods. Ultra-high vacuum experiments were performed to investigate the 200 keV H+ radiolysis chemistry of predeposited C2H2:H2O ices, both as mixed and layered geometries. Fourier-transform infrared spectroscopy was used to monitor in situ newly formed species as a function of the accumulated energy dose (or H+ fluence). The infrared spectral assignments are further confirmed in isotope labeling experiments using H218O. Results. The energetic processing of C2H2:H2O ice not only results in the formation of (semi-) saturated hydrocarbons (C2H4 and C2H6) and polyynes as well as cumulenes (C4H2 and C4H4), but it also efficiently forms O-bearing COMs, including vinyl alcohol, ketene, acetaldehyde, and ethanol, for which the reaction cross-section and product composition are derived. A clear composition transition of the product, from H-poor to H-rich species, is observed as a function of the accumulated energy dose. Furthermore, the astronomical relevance of the resulting reaction network is discussed.
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Marks, Joshua H., Jia Wang, Mikhail M. Evseev, Oleg V. Kuznetsov, Ivan O. Antonov y Ralf I. Kaiser. "Complex Reactive Acids from Methanol and Carbon Dioxide Ice: Glycolic Acid (HOCH2COOH) and Carbonic Acid Monomethyl Ester (CH3OCOOH)". Astrophysical Journal 942, n.º 1 (1 de enero de 2023): 43. http://dx.doi.org/10.3847/1538-4357/ac97e3.
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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 C2H4O3 were 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.
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Cassone, Giuseppe, Franz Saija, Jiri Sponer, Judit E. Sponer, Antonio Jiménez-Escobar, Angela Ciaravella y Cesare Cecchi-Pestellini. "Atomistic simulations of the free-energy landscapes of interstellar chemical reactions: the case of methyl isocyanate". Monthly Notices of the Royal Astronomical Society 504, n.º 2 (9 de abril de 2021): 1565–70. http://dx.doi.org/10.1093/mnras/stab958.
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ABSTRACT Although complex organic molecules are observed in a wide variety of environments, chemical reaction networks heading to their formation are higly debated. It is a major endeavour to model the rates of reactions and incorporate them into chemical networks. The vast majority of the computational investigations in astrochemistry take into consideration oversimplified molecular models where chemical reactions are simulated under vacuum conditions (gas phase) and with crudely approximated entropic contributions to the free energy. We use density functional theory-based molecular dynamics techniques coupled with state-of-the-art metadynamics methods to investigate the role of ices embedding the reactants in shaping the free-energy landscape of selected reactions. Ices are chemically defined at the same level of theory of the reactants themselves. We consider as test case the transformation of methane and isocyanic acid into molecular hydrogen and methyl isocyanate, a species bearing similarities with peptide bonds. We examine the thermodynamically unfavoured case of very stable reactants to magnify modifications in the energy configuration induced by a solid amorphous water ice, either pure or mixed with CO. The presence of an active medium modifies significantly the free-energy surface, widening the path connecting reactants and products, and decreasing substantially the energy barriers. Ices not only act as gatherers of reactants, but also create thermodynamic conditions favouring chemical evolution.
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Biver, Nicolas, Dominique Bockelée-Morvan, Raphaël Moreno, Jacques Crovisier, Pierre Colom, Dariusz C. Lis, Aage Sandqvist, Jérémie Boissier, Didier Despois y Stefanie N. Milam. "Ethyl alcohol and sugar in comet C/2014 Q2 (Lovejoy)". Science Advances 1, n.º 9 (octubre de 2015): e1500863. http://dx.doi.org/10.1126/sciadv.1500863.
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The presence of numerous complex organic molecules (COMs; defined as those containing six or more atoms) around protostars shows that star formation is accompanied by an increase of molecular complexity. These COMs may be part of the material from which planetesimals and, ultimately, planets formed. Comets represent some of the oldest and most primitive material in the solar system, including ices, and are thus our best window into the volatile composition of the solar protoplanetary disk. Molecules identified to be present in cometary ices include water, simple hydrocarbons, oxygen, sulfur, and nitrogen-bearing species, as well as a few COMs, such as ethylene glycol and glycine. We report the detection of 21 molecules in comet C/2014 Q2 (Lovejoy), including the first identification of ethyl alcohol (ethanol, C2H5OH) and the simplest monosaccharide sugar glycolaldehyde (CH2OHCHO) in a comet. The abundances of ethanol and glycolaldehyde, respectively 5 and 0.8% relative to methanol (0.12 and 0.02% relative to water), are somewhat higher than the values measured in solar-type protostars. Overall, the high abundance of COMs in cometary ices supports the formation through grain-surface reactions in the solar system protoplanetary disk.