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1

Rojas-García, O. S., A. I. Gómez-Ruiz, A. Palau, M. T. Orozco-Aguilera, M. Chavez Dagostino, and S. E. Kurtz. "Interstellar Complex Organic Molecules in SiO-traced Massive Outflows." Astrophysical Journal Supplement Series 262, no. 1 (August 19, 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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2

Vazart, Fanny, Cecilia Ceccarelli, Nadia Balucani, and Dimitrios Skouteris. "Quantum Chemical Computations of Gas-phase Glycolaldehyde Deuteration and Constraints on Its Formation Route." Astrophysical Journal 941, no. 2 (December 1, 2022): 196. http://dx.doi.org/10.3847/1538-4357/aca3a3.

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Abstract Despite the detection of numerous interstellar complex organic molecules (iCOMs) for decades, it is still a matter of debate whether they are synthesized in the gas phase or on the icy surface of interstellar grains. In the past, molecular deuteration has been used to constrain the formation paths of small and abundant hydrogenated interstellar species. More recently, the deuteration degree of formamide, one of the most interesting iCOMs, has also been explained with the hypothesis that it is formed by the gas-phase reaction NH2 + H2CO. In this paper, we aim at using molecular deuteration to constrain the formation of another iCOM, glycolaldehyde, which is an important prebiotic species. More specifically, we have performed dedicated electronic structure and kinetic calculations to establish the glycolaldehyde deuteration degree in relation to that of ethanol, which is its possible parent species according to the suggestion of Skouteris et al. We found that the abundance ratio of the species containing one D atom over the all-protium counterpart depends on the produced D isotopomer and varies from 0.9 to 0.5. These theoretical predictions compare extremely well with the monodeuterated isotopomers of glycolaldehyde and that of ethanol measured toward the solar-like protostar IRAS 16293–2422, supporting the hypothesis that glycolaldehyde could be produced in the gas phase for this source. In addition, the present work confirms that the deuterium fractionation of iCOMs cannot be simply anticipated based on the deuterium fractionation of the parent species but necessitates a specific study, as already shown for the case of formamide.
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3

Bianchi, Eleonora. "Interstellar complex organic molecules in the prototypical Class I protostar SVS13-A: From large scales to planet forming disks." EPJ Web of Conferences 265 (2022): 00028. http://dx.doi.org/10.1051/epjconf/202226500028.

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We present a chemical systematic study of the Class I object SVS13- A obtained in the framework of two IRAM Large Programs: ASAI (Astrochemical Survey At IRAM-30m) with the 30m and SOLIS (Seeds Of Life In Space) with NOEMA. Thanks to the ASAI high-sensitivity unbiased spectral survey of the 3, 2 and 1.3mm bands, we detect and analyse several emission lines from deuterated species and interstellar complex organic molecules (iCOMs, e.g. molecules composed by 6 or more atoms and based on carbon). Within SOLIS, we obtain high-sensitivity and high-spatial resolution (∼ 180 au) maps of crucial iCOMs. As a follow up, thanks to ALMA we explore the chemistry in the planet forming region (∼ 50 au). We image emission lines from methanol (CH3OH), acetaldehyde (CH3CHO), formamide (NH2CHO) and dimethyl ether (CH3OCH3). The different spatial distributions suggest a chemical differentiation inside the binary system or a different continuum opacity in the two protostellar disks.
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4

López-Sepulcre, Ana, and 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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Enrique-Romero, Joan, Albert Rimola, Cecilia Ceccarelli, Piero Ugliengo, Nadia Balucani, and Dimitrios Skouteris. "Quantum Mechanical Simulations of the Radical–Radical Chemistry on Icy Surfaces." Astrophysical Journal Supplement Series 259, no. 2 (March 22, 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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6

Puzzarini, Cristina, Zoi Salta, Nicola Tasinato, Jacopo Lupi, Carlo Cavallotti, and Vincenzo Barone. "A twist on the reaction of the CN radical with methylamine in the interstellar medium: new hints from a state-of-the-art quantum-chemical study." Monthly Notices of the Royal Astronomical Society 496, no. 4 (June 16, 2020): 4298–310. http://dx.doi.org/10.1093/mnras/staa1652.

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ABSTRACT Despite the fact that the majority of current models assume that interstellar complex organic molecules (iCOMs) are formed on dust–grain surfaces, there is some evidence that neutral gas-phase reactions play an important role. In this paper, we investigate the reaction occurring in the gas phase between methylamine (CH3NH2) and the cyano (CN) radical, for which only fragmentary and/or inaccurate results have been reported to date. This case study allows us to point out the pivotal importance of employing quantum-chemical calculations at the state of the art. Since the two major products of the CH3NH2 + CN reaction, namely the CH3NH and CH2NH2 radicals, have not been spectroscopically characterized yet, some effort has been made for filling this gap.
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7

Chahine, L., A. López-Sepulcre, R. Neri, C. Ceccarelli, S. Mercimek, C. Codella, M. Bouvier, et al. "Organic chemistry in the protosolar analogue HOPS-108: Environment matters." Astronomy & Astrophysics 657 (January 2022): A78. http://dx.doi.org/10.1051/0004-6361/202141811.

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Context. Hot corinos are compact regions around solar-mass protostellar objects that are very rich in interstellar Complex Organic Molecules (iCOMs). How the abundance of these molecules is affected by the environmental physical conditions is still an open question. More specifically, addressing this point is key to understand our own chemical origins since the Solar System formed in a large cluster of low- to high-mass stars and was therefore subject to external heating and ultraviolet irradiation which may have shaped the chemistry of its early formation stages. Aims. The goal of this high resolution study is to determine the abundance ratios of iCOMs in HOPS-108, which is a Class 0 protostar and a hot corino candidate located in the nearest Solar System analogue, the protostellar cluster OMC-2 FIR 4, in Orion. We aim to compare the abundance ratios to those found in other hot corinos, which are all located in less crowded environments, in order to understand the impact of environmental conditions on hot corinos’ chemistry. Methods. We observed the OMC-2 FIR 4 proto-cluster using the Band 6 of the Atacama Large (sub-)Millimetre Array in Cycle 4 with an angular resolution of ~0.′′28 (110 au). We determined the abundances and temperature of the species using local thermodynamic equilibrium (LTE) and non-LTE analysis. Results. Our results reveal a rich organic chemistry towards HOPS-108, asserting that it is a hot corino where the following iCOMs are detected: CH3OH, HCOOCH3, CH3OCH3, CH318OH, CH2DOH, CH3COCH3, CH3CHO, CH3CN, 13CH3CN, C2H5CN, and NH2CHO. Remarkably, we find a possible enhancement in the HCOOCH3 abundance with respect to other known hot corinos. Indeed, the [CH3OCH3]/[HCOOCH3] abundance ratio in this source is ~0.2 and, within the uncertainties, it deviates from the known correlation marginally where [CH3OCH3]/[HCOOCH3] ~1. A relatively low [CH2DOH]/[CH3OH] abundance ratio of ~0.02 is also obtained, which is in agreement with that found in another Orion source, HH212, suggesting a higher gas temperature during the early phases of ice mantle formation. Conclusions. The [CH3OCH3]/[HCOOCH3] and [CH2DOH]/[CH3OH] abundance ratios in HOPS-108 might result from different physical conditions in the Orion molecular complex compared to other regions. The former ratio cannot be reproduced with current chemical models, highlighting the importance of improving the chemical networks with theoretical calculations. More hot corinos located in heavily clustered regions such as Orion should be targeted in order to measure these ratios and evaluate whether they are an environmental product or whether HOPS-108 is an exceptional hot corino overall.
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8

Imai, Muneaki, Yoko Oya, Brian Svoboda, Hauyu Baobab Liu, Bertrand Lefloch, Serena Viti, Yichen Zhang, et al. "Chemical and Physical Characterization of the Isolated Protostellar Source CB68: FAUST IV." Astrophysical Journal 934, no. 1 (July 1, 2022): 70. http://dx.doi.org/10.3847/1538-4357/ac77e7.

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Abstract The chemical diversity of low-mass protostellar sources has so far been recognized, and environmental effects are invoked as its origin. In this context, observations of isolated protostellar sources without the influence of nearby objects are of particular importance. Here, we report the chemical and physical structures of the low-mass Class 0 protostellar source IRAS 16544−1604 in the Bok globule CB 68, based on 1.3 mm Atacama Large Millimeter/submillimeter Array observations at a spatial resolution of ∼70 au that were conducted as part of the large program FAUST. Three interstellar saturated complex organic molecules (iCOMs), CH3OH, HCOOCH3, and CH3OCH3, are detected toward the protostar. The rotation temperature and the emitting region size for CH3OH are derived to be 131 ± 11 K and ∼10 au, respectively. The detection of iCOMs in close proximity to the protostar indicates that CB 68 harbors a hot corino. The kinematic structure of the C18O, CH3OH, and OCS lines is explained by an infalling–rotating envelope model, and the protostellar mass and the radius of the centrifugal barrier are estimated to be 0.08–0.30 M ⊙ and <30 au, respectively. The small radius of the centrifugal barrier seems to be related to the small emitting region of iCOMs. In addition, we detect emission lines of c-C3H2 and CCH associated with the protostar, revealing a warm carbon-chain chemistry on a 1000 au scale. We therefore find that the chemical structure of CB 68 is described by a hybrid chemistry. The molecular abundances are discussed in comparison with those in other hot corino sources and reported chemical models.
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9

Ascenzi, Daniela, Andrea Cernuto, Nadia Balucani, Paolo Tosi, Cecilia Ceccarelli, Luca Matteo Martini, and Fernando Pirani. "Destruction of dimethyl ether and methyl formate by collisions with He+." Astronomy & Astrophysics 625 (May 2019): A72. http://dx.doi.org/10.1051/0004-6361/201834585.

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Context. To correctly model the abundances of interstellar complex organic molecules (iCOMs) in different environments, both formation and destruction routes should be appropriately accounted for. While several scenarios have been explored for the formation of iCOMs via grain and gas-phase processes, much less work has been devoted to understanding the relevant destruction pathways, with special reference to (dissociative) charge exchange or proton transfer reactions with abundant atomic and molecular ions such as He+, H3+ and HCO+. Aims. By using a combined experimental and theoretical methodology we provide new values for the rate coefficients and branching ratios (BRs) of the reactions of He+ ions with two important iCOMs, namely dimethyl ether (DME) and methyl formate (MF). We also review the destruction routes of DME and MF by other two abundant ions, namely H3+ and HCO+. Methods. Based on our recent laboratory measurements of cross sections and BRs for the DME/MF + He+ reactions over a wide collision energy, we extended our theoretical insights on the selectivity of the microscopic dynamics to calculate the rate coefficients k(T) in the temperature range from 10 to 298 K. We implemented these new and revised kinetic data in a general model of cold and warm gas, simulating environments where DME and MF have been detected. Results. Due to stereodynamical effects present at low collision energies, the rate coefficients, BRs and temperature dependences here proposed differ substantially from those reported in KIDA and UDfA, two of the most widely used astrochemical databases. These revised rates impact the predicted abundances of DME and MF, with variations up to 40% in cold gases and physical conditions similar to those present in prestellar cores. Conclusions. This work demonstrates that the accuracy of astrochemical models can be improved by a thorough characterisation of the destruction routes of iCOMs. The details of the chemical systems can, indeed, strongly affect their efficiency and significant deviations with respect to the commonly used Langevin model estimates are possible.
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10

De Simone, M., C. Codella, C. Ceccarelli, A. López-Sepulcre, A. Witzel, R. Neri, N. Balucani, et al. "Seeds of Life in Space (SOLIS)." Astronomy & Astrophysics 640 (August 2020): A75. http://dx.doi.org/10.1051/0004-6361/201937004.

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Context. The interstellar complex organic molecules (iCOMs) are C-bearing molecules containing at least six atoms; two main proposals for their formation are suggested: a direct formation in the icy mantle of the dust grains and formation through the reaction in gas phase of released grain mantle species. The shocked gas along outflows driven by low-mass protostars is a unique environment to study how the iCOMs can be formed as the composition of the dust mantles is sputtered into the gas phase. Aims. The chemical richness in shocked material associated with low-mass protostellar outflows has been so far studied in the prototypical L1157 blue-shifted outflow to investigate the iCOM formation routes. To understand whether the case of L1157-B1 is unique, we imaged and studied the IRAS 4A outflows in the NGC 1333 star forming region. Methods. We used the NOrthern Extended Millimeter Array interferometer as part of the IRAM Seeds Of Life in Space (SOLIS) Large Program to image the large-scale bipolar outflows driven by the IRAS 4A system in the 3 mm band, and we compared the observation with the GRAINOBLE+ astrochemical model. Results. We report the first detection, in the IRAS 4A outflows, of several iCOMs: six lines of methanol (CH3OH), eight of acetaldehyde (CH3CHO), one of formamide (NH2CHO), and four of dimethyl ether (CH3OCH3), all sampling upper excitation energy up to ~30 K. We found a significant chemical differentiation between the southeast outflow driven by the IRAS 4A1 protostar, showing a richer molecular content, and the north–southwest one driven by the IRAS 4A2 hot corino. The CH3OH/CH3CHO abundance ratio is lower by a factor of ~4 in the former; furthermore, the ratio in the IRAS 4A outflows is lower by a factor of ~10 with respect to the values found in different hot corinos. Conclusions. After L1157-B1, the IRAS 4A outflow is now the second outflow to show an evident chemical complexity. Given that CH3OH is a grain surface species, the astrochemical gas-phase model run with GRAINOBLE+ reproduced our observation assuming that acetaldehyde is formed mainly through the gas-phase reaction of the ethyl radical (CH3CH2) and atomic oxygen. Furthermore, the chemical differentiation between the two outflows suggests that the IRAS 4A1 outflow is likely younger than that of the IRAS 4A2. Further investigation is needed to constrain the age of the outflow. In addition, observation of even younger shocks are necessary. In order to provide strong constraints on the CH3CHO formation mechanisms it would be interesting to observe CH3CH2, but given that its frequencies are not known, future spectroscopic studies on this species are needed.
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11

Mercimek, S., C. Codella, L. Podio, E. Bianchi, L. Chahine, M. Bouvier, A. López-Sepulcre, R. Neri, and C. Ceccarelli. "Chemical survey of Class I protostars with the IRAM-30 m." Astronomy & Astrophysics 659 (March 2022): A67. http://dx.doi.org/10.1051/0004-6361/202141790.

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Context. Class I protostars are a bridge between Class 0 protostars (≤105 yr old), and Class II (≥106 yr) protoplanetary disks. Recent studies show gaps and rings in the dust distribution of disks younger than 1 Myr, suggesting that planet formation may start already at the Class I stage. To understand what chemistry planets will inherit, it is crucial to characterize the chemistry of Class I sources and to investigate how chemical complexity evolves from Class 0 protostars to protoplanetary disks. Aims. There are two goals: (i) to perform a census of the molecular complexity in a sample of four Class I protostars, and (ii) to compare the data with the chemical compositions of earlier and later phases of the Sun-like star formation process. Methods. We performed IRAM-30 m observations at 1.3 mm towards four Class I objects (L1489-IRS, B5-IRS1, L1455-IRS1, and L1551-IRS5). The column densities of the detected species were derived assuming local thermodynamic equilibrium (LTE) or large velocity gradients (LVGs). Results. We detected 27 species: C-chains, N-bearing species, S-bearing species, Si-bearing species, deuterated molecules, and interstellar complex organic molecules (iCOMs; CH3OH, CH3CN, CH3CHO, and HCOOCH3). Among the members of the observed sample, L1551-IRS5 is the most chemically rich source. Different spectral profiles are observed: (i) narrow lines (~1 km s−1) towards all the sources, (ii) broader lines (~4 km s−1) towards L1551-IRS5, and (iii) line wings due to outflows (in B5-IRS1, L1455-IRS1, and L1551-IRS5). Narrow c-C3H2 emission originates from the envelope with temperatures of 5–25 K and sizes of ~2′′−10′′. The iCOMs in L1551-IRS5 reveal the occurrence of hot corino chemistry, with CH3OH and CH3CN lines originating from a compact (~0.′′15) and warm (T > 50 K) region. Finally, OCS and H2S seem to probe the circumbinary disks in the L1455-IRS1 and L1551-IRS5 binary systems. The deuteration in terms of elemental D/H in the molecular envelopes is: ~10−70% (D2CO/H2CO), ~5−15% (HDCS/H2CS), and ~1−23% (CH2DOH/CH3OH). For the L1551-IRS5 hot corino we derive D/H ~2% (CH2DOH/CH3OH). Conclusions. Carbon chain chemistry in extended envelopes is revealed towards all the sources. In addition, B5-IRS1, L1455-IRS1, and L1551-IRS5 show a low-excitation methanol line that is narrow and centered at systemic velocity, suggesting an origin from an extended structure, plausibly UV-illuminated. The abundance ratios of CH3CN, CH3CHO, and HCOOCH3 with respect to CH3OH measured towards the L1551-IRS5 hot corino are comparable to that estimated at earlier stages (prestellar cores, Class 0 protostars), and to that found in comets. The deuteration in our sample is also consistent with the values estimated for sources at earlier stages. These findings support the inheritance scenario from prestellar cores to the Class I phase when planets start forming.
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12

Herbst, Eric, and Ewine F. van Dishoeck. "Complex Organic Interstellar Molecules." Annual Review of Astronomy and Astrophysics 47, no. 1 (September 2009): 427–80. http://dx.doi.org/10.1146/annurev-astro-082708-101654.

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13

Álvarez-Barcia, S., P. Russ, J. Kästner, and T. Lamberts. "Hydrogen transfer reactions of interstellar complex organic molecules." Monthly Notices of the Royal Astronomical Society 479, no. 2 (June 6, 2018): 2007–15. http://dx.doi.org/10.1093/mnras/sty1478.

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14

Dartois, E., M. Chabot, T. Id Barkach, H. Rothard, B. Augé, A. N. Agnihotri, A. Domaracka, and P. Boduch. "Non-thermal desorption of complex organic molecules." Astronomy & Astrophysics 627 (July 2019): A55. http://dx.doi.org/10.1051/0004-6361/201834787.

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Context. The occurrence of complex organic molecules (COMs) in the gas phase at low temperature in the dense phases of the interstellar medium suggests that a non-thermal desorption mechanism is at work because otherwise, COMs should condense within a short timescale onto dust grains. Vacuum ultraviolet (VUV) photodesorption has been shown to be much less efficient for complex organic molecules, such as methanol, because mostly photoproducts are ejected. The induced photolysis competes with photodesorption for large COMs, which considerably lowers the efficiency to desorb intact molecules. Aims. We pursue an experimental work that has already shown that water molecules, the dominant ice mantle species, can be efficiently sputtered by cosmic rays. We investigate the sputtering efficiency of complex organic molecules that are observed either in the ice mantles of interstellar dense clouds directly by infrared spectroscopy (CH3OH), or that are observed in the gas phase by millimeter telescopes (CH3COOCH3) and that could be released from interstellar grain surfaces. Methods. We irradiated ice films containing complex organic molecules (methanol and methyl acetate) and water with swift heavy ions in the electronic sputtering regime. We monitored the infrared spectra of the film as well as the species released to the gas phase with a mass spectrometer. Results. We demonstrate that when methanol or methyl acetate is embedded in a water-ice mantle exposed to cosmic rays, a large portion is sputtered as an intact molecule, with a sputtering yield close to that of the main water-ice matrix. This must be even more true for the case of more volatile ice matrices, such as those that are embedded in carbon monoxide. Conclusions. Cosmic rays penetrating deep into dense clouds provide an efficient mechanism to desorb complex organic molecules. Compared to the VUV photons, which are induced by the interaction of cosmic rays, a large portion desorb as intact molecules with a proportion corresponding to the time-dependent bulk composition of the ice mantle, the latter evolving with time as a function of fluence due to the radiolysis of the bulk.
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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, and 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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Lattelais, M., F. Pauzat, Y. Ellinger, and C. Ceccarelli. "INTERSTELLAR COMPLEX ORGANIC MOLECULES AND THE MINIMUM ENERGY PRINCIPLE." Astrophysical Journal 696, no. 2 (April 17, 2009): L133—L136. http://dx.doi.org/10.1088/0004-637x/696/2/l133.

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Greenberg, J. Mayo, and Willem Schutte. "Infrared Spectral Identification of Complex Organic Molecules in Interstellar Grains." Symposium - International Astronomical Union 112 (1985): 145–50. http://dx.doi.org/10.1017/s0074180900146455.

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The chemical evolution of interstellar grains leads ultimately to a composition consisting largely of complex organic molecules. Comparison of infrared absorption spectra of laboratory produced analogue materials with astronomical observations confirm the presence of similar molecules in interstellar space. The abundance of this complex organic matter derived from the strength of the absorption bands is of the order of ten million solar masses and is almost certainly as large or larger than all conceivable planets.
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18

Öberg, Karin I. "Photochemistry and Astrochemistry: Photochemical Pathways to Interstellar Complex Organic Molecules." Chemical Reviews 116, no. 17 (April 21, 2016): 9631–63. http://dx.doi.org/10.1021/acs.chemrev.5b00694.

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19

Dartois, E., M. Chabot, A. Bacmann, P. Boduch, A. Domaracka, and H. Rothard. "Non-thermal desorption of complex organic molecules." Astronomy & Astrophysics 634 (February 2020): A103. http://dx.doi.org/10.1051/0004-6361/201936934.

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Aims. Methanol ice is embedded in interstellar ice mantles present in dense molecular clouds. We aim to measure the sputtering efficiencies starting from different ice mantles of varying compositions experimentally, in order to evaluate their potential impact on astrochemical models. The sputtering yields of complex organic molecules is of particular interest, since few mechanisms are efficient enough to induce a significant feedback to the gas phase. Methods. We irradiated ice film mixtures made of methanol and carbon dioxide of varying ratios with swift heavy ions in the electronic sputtering regime. We monitored the evolution of the infrared spectra as well as the species released to the gas phase with a mass spectrometer. Methanol (12C) and isotopically labelled 13C-methanol were used to remove any ambiguity on the measured irradiation products. Results. The sputtering of methanol embedded in carbon dioxide ice is an efficient process leading to the ejection of intact methanol in the gas phase. We establish that when methanol is embedded in a carbon-dioxide-rich mantle exposed to cosmic rays, a significant fraction (0.2–0.3 in this work) is sputtered as intact molecules. The sputtered fraction follows the time-dependent bulk composition of the ice mantle, the latter evolving with time due to the radiolysis-induced evolution of the bulk. If methanol is embedded in a carbon dioxide ice matrix, as the analyses of the spectral shape of the CO2 bending mode observations in some lines of sight suggest, the overall methanol sputtering yield is higher than if embedded in a water ice mantle. The sputtering is increased by a factor close to the dominant ice matrix sputtering yield, which is about six times higher for pure carbon dioxide ice when compared to water ice. These experiments are further constraining the cosmic-ray-induced ice mantle sputtering mechanisms important role in the gas-phase release of complex organic molecules from the interstellar solid phase.
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Abplanalp, Matthew J., Samer Gozem, Anna I. Krylov, Christopher N. Shingledecker, Eric Herbst, and 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, no. 28 (July 5, 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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21

Theulé, Patrice. "Chemical dynamics in interstellar ice." Proceedings of the International Astronomical Union 15, S350 (April 2019): 139–43. http://dx.doi.org/10.1017/s1743921319008342.

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AbstractChemistry in the interstellar medium is generally out-of-equilibrium and as such is kinetically controlled by a set of time-dependent equations, both for gas-phase chemistry and solid-state chemistry. The competition between the different possible reactions will determine toward which complex molecules the chemical network is driven to. The formation of complex molecules on the surface of the grains or in the ice mantle covering them is set by the diffusion-reaction equation, which is depending on temperature dependent reaction rate constants and diffusion coefficients. This paper shows how these two parameters can be experimentally determined by laboratory experiments. It also shows how the ice mantle reorganization plays an important role in the trapping and reactivity, which leads to the formation of complex organic molecules.
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22

Allamandola, Louis J., Max P. Bernstein, and Scott A. Sandford. "Photochemical Evolution of Interstellar/Precometary Organic Material." International Astronomical Union Colloquium 161 (January 1997): 23–47. http://dx.doi.org/10.1017/s0252921100014585.

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AbstractInfrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Since comets are thought to be a major source of the volatiles on the primative earth, their organic inventory is of central importance to questions concerning the origin of life. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, CH4, H2, and probably some NH3and H2CO, as well as more complex species including nitriles, ketones, and esters. The evidence for these, as well as carbonrich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon is briefly reviewed. This is followed by a detailed summary of interstellar/precometary ice photochemical evolution based on laboratory studies of realistic polar ice analogs. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(= O)NH2(formamide), CH3C(= O)NH2(acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including polyoxymethylene and related species (POMs), amides, and ketones. The ready formation of these organic species from simple starting mixtures, the ice chemistry that ensues when these ices are mildly warmed, plus the observation that the more complex refractory photoproducts show lipid-like behavior and readily self organize into droplets upon exposure to liquid water suggest that comets may have played an important role in the origin of life.
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23

Lattelais, M., M. Bertin, H. Mokrane, C. Romanzin, X. Michaut, P. Jeseck, J. H. Fillion, et al. "Differential adsorption of complex organic molecules isomers at interstellar ice surfaces." Astronomy & Astrophysics 532 (July 12, 2011): A12. http://dx.doi.org/10.1051/0004-6361/201016184.

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24

Suzuki, H., M. Ohishi, M. Morimoto, N. Kaifu, P. Friberg, W. M. Irvine, H. E. Matthews, and S. Saito. "Recent Observations of Organic Molecules in Nearby Cold, Dark Interstellar Clouds." Symposium - International Astronomical Union 112 (1985): 139–44. http://dx.doi.org/10.1017/s0074180900146443.

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We report recent investigations of the organic chemistry of relatively nearby cold, dark interstellar clouds. Specifically, we confirm the presence of interstellar tricarbon monoxide (C3O) in Taurus Molecular Cloud1 (TMC-1); report the first detection in such regions of acetaldehyde (CH3CHO), the most complex oxygen-containing organic molecule yet found in dark clouds; report the first astronomical detection of several molecular rotational transitions, including the J=18−17 and 14−13 transitions of cyanodiacetylene (HC5N), the 101−000 transition of acetaldehyde, and the J=5−4 transition of C3O; and set a significant upper limit on the abundance of cyanocarbene (HCCN) as a result of the first reported interstellar search for this molecule.
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25

Ghesquière, P., A. Ivlev, J. A. Noble, and P. Theulé. "Reactivity in interstellar ice analogs: role of the structural evolution." Astronomy & Astrophysics 614 (June 2018): A107. http://dx.doi.org/10.1051/0004-6361/201732288.

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Context. The synthesis of interstellar complex organic molecules in ice involves several types of reactions between molecules and/or radicals that are usually considered to be diffusion controlled. Aims. We aim to understand the coupling between diffusion and reactivity in the interstellar ice mantle using a model binary reaction in the diffusion-limited regime. Methods. We performed isothermal kinetic laboratory experiments on interstellar ice analogs at low temperatures, using the NH3:CO2:H2O model system where reactants NH3 and CO2 have a low reaction barrier and are diluted in a water-dominated ice. Results. We found that in the diffusion-limited regime, the reaction kinetics is not determined by the intrinsic bulk diffusivity of reactants. Instead, reactions are driven by structural changes evolving in amorphous water ice, such as pore collapse and crystallization. Diffusion of reactants in this case likely occurs along the surface of (tiny) cracks generated by the structural changes. Conclusions. The reactivity driven by the structural changes breaks the conventional picture of reactant molecules/radicals diffusing in a bulk water ice. This phenomenon is expected to lead to a dramatic increase in production rates of interstellar complex organic molecules in star-forming regions.
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26

Ehrenfreund, Pascale, Marco Spaans, and Nils G. Holm. "The evolution of organic matter in space." Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 369, no. 1936 (February 13, 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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Krim, Lahouari, Mindaugas Jonusas, Jean-Claude Guillemin, Manuel Yáñez, and Al Mokhtar Lamsabhi. "Reduction of CO functional groups through H addition reactions: a comparative study between H2CO + H, CH3CH2CHO + H and CH3OCHO + H under interstellar conditions." Physical Chemistry Chemical Physics 20, no. 30 (2018): 19971–78. http://dx.doi.org/10.1039/c8cp03249a.

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28

Hasegawa, Tatsuhiko I., Eric Herbst, and Chun M. Leukng. "Models of gas-grain chemistry in dense interstellar clouds with complex organic molecules." Astrophysical Journal Supplement Series 82 (September 1992): 167. http://dx.doi.org/10.1086/191713.

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29

Hudgins, D. M., L. J. Allamandola, and S. A. Sandford. "Complex organic molecules in space: The carriers of the interstellar infrared emission features." Advances in Space Research 19, no. 7 (January 1997): 999–1008. http://dx.doi.org/10.1016/s0273-1177(97)00341-4.

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30

Agúndez, M., N. Marcelino, B. Tercero, C. Cabezas, P. de Vicente, and J. Cernicharo. "O-bearing complex organic molecules at the cyanopolyyne peak of TMC-1: Detection of C2H3CHO, C2H3OH, HCOOCH3, and CH3OCH3." Astronomy & Astrophysics 649 (May 2021): L4. http://dx.doi.org/10.1051/0004-6361/202140978.

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We report the detection of the oxygen-bearing complex organic molecules propenal (C2H3CHO), vinyl alcohol (C2H3OH), methyl formate (HCOOCH3), and dimethyl ether (CH3OCH3) toward the cyanopolyyne peak of the starless core TMC-1. These molecules were detected through several emission lines in a deep Q-band line survey of TMC-1 carried out with the Yebes 40m telescope. These observations reveal that the cyanopolyyne peak of TMC-1, which is a prototype of a cold dark cloud rich in carbon chains, also contains O-bearing complex organic molecules such as HCOOCH3 and CH3OCH3, which have previously been seen in a handful of cold interstellar clouds. In addition, this is the first secure detection of C2H3OH in space and the first time that C2H3CHO and C2H3OH have been detected in a cold environment, adding new pieces to the puzzle of complex organic molecules in cold sources. We derive column densities of (2.2 ± 0.3) × 1011 cm−2, (2.5 ± 0.5) × 1012 cm−2, (1.1 ± 0.2) × 1012 cm−2, and (2.5 ± 0.7) × 1012 cm−2 for C2H3CHO, C2H3OH, HCOOCH3, and CH3OCH3, respectively. Interestingly, C2H3OH has an abundance similar to that of its well-known isomer acetaldehyde (CH3CHO), with C2H3OH/CH3CHO ∼ 1 at the cyanopolyyne peak. We discuss potential formation routes to these molecules and recognize that further experimental, theoretical, and astronomical studies are needed to elucidate the true formation mechanism of these O-bearing complex organic molecules in cold interstellar sources.
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31

Duvernay, F., A. Rimola, P. Theule, G. Danger, T. Sanchez, and T. Chiavassa. "Formaldehyde chemistry in cometary ices: the case of HOCH2OH formation." Phys. Chem. Chem. Phys. 16, no. 44 (2014): 24200–24208. http://dx.doi.org/10.1039/c4cp03031a.

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Laboratory experiments devoted to simulate the chemistry occurring in interstellar and cometary ice analogues are of paramount importance to understand the formation of complex organic molecules that are detected throughout the universe.
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32

Belloche, Arnaud. "Molecular complexity in the interstellar medium." Proceedings of the International Astronomical Union 15, S350 (April 2019): 96–99. http://dx.doi.org/10.1017/s1743921319006380.

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AbstractThe search for complex organic molecules in the interstellar medium (ISM) has revealed species of ever greater complexity. This search relies on the progress made in the laboratory to characterize their rotational spectra. Our understanding of the processes that lead to molecular complexity in the ISM builds on numerical simulations that use chemical networks fed by laboratory and theoretical studies. The advent of ALMA and NOEMA has opened a new door to explore molecular complexity in the ISM. Their high angular resolution reduces the spectral confusion of star-forming cores and their increased sensitivity allows the detection of low-abundance molecules that could not be probed before. The complexity of the recently-detected molecules manifests itself not only in terms of number of atoms but also in their molecular structure. We discuss these developments and report on ReMoCA, a new spectral line survey performed with ALMA toward the high-mass star-forming region Sgr B2(N).
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33

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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34

Leroux, Killian, and Lahouari Krim. "Thermal and photochemical study of CH3OH and CH3OH–O2 astrophysical ices." Monthly Notices of the Royal Astronomical Society 500, no. 1 (October 20, 2020): 1188–200. http://dx.doi.org/10.1093/mnras/staa3205.

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ABSTRACT Methanol, which is one of the most abundant organic molecules in the interstellar medium, plays an important role in the complex grain surface chemistry that is believed to be a source of many organic compounds. Under energetic processing such as ultraviolet (UV) photons or cosmic rays, methanol may decompose into CH4, CO2, CO, HCO, H2CO, CH3O and CH2OH, which in turn lead to complex organic molecules such as CH3OCHO, CHOCH2OH and HOCH2CH2OH through radical recombination reactions. However, although molecular oxygen and its detection, abundance and role in the interstellar medium have been the subject of many debates, few experiments on the oxidation of organic compounds have been carried out under interstellar conditions. The present study shows the behaviour of solid methanol when treated by UV light and thermal processing in oxygen-rich environments. Methanol has been irradiated in the absence and presence of O2 at different concentrations in order to study how oxidized complex organic molecules may form and also to investigate the O-insertion reaction in the C–H bound to form methanediol HOCH2OH through a CH3OH + O(1D) solid-state reaction. The adding of O2 in the thermal and photochemical reaction of solid methanol leads to the formation of O3, H2O and HO2, in addition to three main organics, HCOOH, CHOCHO and HOCH2OH. We show that in an O2-rich environment, species such as CO, CH4, HCO, CH3OH and CHOCH2OH are oxidized into CO2, CH3OH, HC(O)OO, HOCH2OH and CHOCHO, respectively, while HCOOH might be formed through the H2CO + O(3P) → (OH + HCO)cage → HCOOH hydrogen-abstraction reaction.
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35

Nuevo, M., U. J. Meierhenrich, L. d’Hendecourt, G. M. Muñoz Caro, E. Dartois, D. Deboffle, W. H. P. Thiemann, J. H. Bredehöft, and L. Nahon. "Enantiomeric separation of complex organic molecules produced from irradiation of interstellar/circumstellar ice analogs." Advances in Space Research 39, no. 3 (January 2007): 400–404. http://dx.doi.org/10.1016/j.asr.2005.05.011.

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36

Shingledecker, C. N., K. L. K. Lee, J. T. Wandishin, N. Balucani, A. M. Burkhardt, S. B. Charnley, R. Loomis, et al. "Detection of interstellar H2CCCHC3N." Astronomy & Astrophysics 652 (August 2021): L12. http://dx.doi.org/10.1051/0004-6361/202140698.

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Context. The chemical pathways linking the small organic molecules commonly observed in molecular clouds to the large, complex, polycyclic species long suspected of being carriers of the ubiquitous unidentified infrared emission bands remain unclear. Aims. To investigate whether the formation of mono- and polycyclic molecules observed in cold cores could form via the bottom-up reaction of ubiquitous carbon-chain species with, for example, atomic hydrogen, a search is made for possible intermediates in data taken as part of the GOTHAM (GBT Observations of TMC-1: Hunting for Aromatic Molecules) project. Methods. Markov chain Monte Carlo (MCMC) source models were run to obtain column densities and excitation temperatures. Astrochemical models were run to examine possible formation routes, including (a) a novel grain-surface pathway involving the hydrogenation of C6N and HC6N, (b) purely gas-phase reactions between C3N and both propyne (CH3CCH) and allene (CH2CCH2), and (c) via the reaction CN + H2CCCHCCH. Results. We report the first detection of cyanoacetyleneallene (H2CCCHC3N) in space toward the TMC-1 cold cloud using the Robert C. Byrd 100 m Green Bank Telescope. Cyanoacetyleneallene may represent an intermediate between less-saturated carbon chains, such as the cyanopolyynes, that are characteristic of cold cores and the more recently discovered cyclic species, such as cyanocyclopentadiene. Results from our models show that the gas-phase allene-based formation route in particular produces abundances of H2CCCHC3N that match the column density of 2 × 1011 cm−2 obtained from the MCMC source model, and that the grain-surface route yields large abundances on ices that could potentially be important as precursors for cyclic molecules.
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Canosa, André. "Gas phase reaction kinetics of complex organic molecules at temperatures of the interstellar medium: The OH + CH3OH case." Proceedings of the International Astronomical Union 15, S350 (April 2019): 35–40. http://dx.doi.org/10.1017/s1743921319006446.

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AbstractRecent experimental and theoretical works concerning gas-phase radical-neutral reactions involving Complex Organic Molecules are reviewed in the context of cold interstellar objects with a special emphasis on the OH + CH3OH reaction and its potential impact on the formation of CH3O.
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38

Fulvio, Daniele, Alexey Potapov, Jiao He, and Thomas Henning. "Astrochemical Pathways to Complex Organic and Prebiotic Molecules: Experimental Perspectives for In Situ Solid-State Studies." Life 11, no. 6 (June 17, 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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Marks, Joshua H., Jia Wang, Mikhail M. Evseev, Oleg V. Kuznetsov, Ivan O. Antonov, and Ralf I. Kaiser. "Complex Reactive Acids from Methanol and Carbon Dioxide Ice: Glycolic Acid (HOCH2COOH) and Carbonic Acid Monomethyl Ester (CH3OCOOH)." Astrophysical Journal 942, no. 1 (January 1, 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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40

Haupa, Karolina Anna, Wei-Siong Ong, and 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, no. 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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41

Scibelli, Samantha, Yancy Shirley, Anton Vasyunin, and Ralf Launhardt. "Detection of complex organic molecules in young starless core L1521E." Monthly Notices of the Royal Astronomical Society 504, no. 4 (April 23, 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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42

Mifsud, Duncan V., Péter Herczku, Béla Sulik, Zoltán Juhász, István Vajda, István Rajta, Sergio Ioppolo, Nigel J. Mason, Giovanni Strazzulla, and Zuzana Kaňuchová. "Proton and Electron Irradiations of CH4:H2O Mixed Ices." Atoms 11, no. 2 (January 22, 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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43

Cecchi-Pestellini, Cesare, Flavio Scappini, Rosalba Saija, Maria Antonia Iatì, Arianna Giusto, Santi Aiello, Ferdinando Borghese, and Paolo Denti. "On the formation and survival of complex prebiotic molecules in interstellar grain aggregates." International Journal of Astrobiology 3, no. 4 (October 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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44

Boamah, Mavis D., Kristal K. Sullivan, Katie E. Shulenberger, ChanMyae M. Soe, Lisa M. Jacob, Farrah C. Yhee, Karen E. Atkinson, Michael C. Boyer, David R. Haines, and Christopher R. Arumainayagam. "Low-energy electron-induced chemistry of condensed methanol: implications for the interstellar synthesis of prebiotic molecules." Faraday Discuss. 168 (2014): 249–66. http://dx.doi.org/10.1039/c3fd00158j.

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In the interstellar medium, UV photolysis of condensed methanol (CH3OH), contained in ice mantles surrounding dust grains, is thought to be the mechanism that drives the formation of “complex” molecules, such as methyl formate (HCOOCH3), dimethyl ether (CH3OCH3), acetic acid (CH3COOH), and glycolaldehyde (HOCH2CHO). The source of this reaction-initiating UV light is assumed to be local because externally sourced UV radiation cannot penetrate the ice-containing dark, dense molecular clouds. Specifically, exceedingly penetrative high-energy cosmic rays generate secondary electrons within the clouds through molecular ionizations. Hydrogen molecules, present within these dense molecular clouds, are excited in collisions with these secondary electrons. It is the UV light, emitted by these electronically excited hydrogen molecules, that is generally thought to photoprocess interstellar icy grain mantles to generate “complex” molecules. In addition to producing UV light, the large numbers of low-energy (<20 eV) secondary electrons, produced by cosmic rays, can also directly initiate radiolysis reactions in the condensed phase. The goal of our studies is to understand the low-energy, electron-induced processes that occur when high-energy cosmic rays interact with interstellar ices, in which methanol, a precursor of several prebiotic species, is the most abundant organic species. Using post-irradiation temperature-programmed desorption, we have investigated the radiolysis initiated by low-energy (7 eV and 20 eV) electrons in condensed methanol at ∼ 85 K under ultrahigh vacuum (5 × 10−10 Torr) conditions. We have identified eleven electron-induced methanol radiolysis products, which include many that have been previously identified as being formed by methanol UV photolysis in the interstellar medium. These experimental results suggest that low-energy, electron-induced condensed phase reactions may contribute to the interstellar synthesis of “complex” molecules previously thought to form exclusively via UV photons.
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45

Rachid, M. G., J. Terwisscha van Scheltinga, D. Koletzki, and H. Linnartz. "Infrared spectra of complex organic molecules in astronomically relevant ice mixtures." Astronomy & Astrophysics 639 (July 2020): A4. http://dx.doi.org/10.1051/0004-6361/202037497.

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Context. Complex organic molecules (COMs) have been largely identified through their characteristic rotational transitions in the gas of interstellar and circumstellar regions. Although these species are formed in the icy mantles that cover dust grains, the most complex species that has been unambiguously identified in the solid-phase to date is methanol (CH3OH). With the upcoming launch of the James Webb Space Telescope (JWST), this situation may change. The higher sensitivity, spectral and spatial resolution of the JWST will allow for the probing of the chemical inventory of ices in star-forming regions. In order to identify features of solid-state molecules in astronomical spectra, laboratory infrared spectra of COMs within astronomically relevant conditions are required. This paper is part of a series of laboratory studies focusing on the infrared spectra of frozen COMs embedded in ice matrices. These reflect the environmental conditions in which COMs are thought to be found. Aims. This work is aimed at characterizing the infrared features of acetone mixed in ice matrices containing H2O, CO2, CO, CH4, and CH3OH for temperatures ranging between 15 K and 160 K. Changes in the band positions and shapes due to variations in the temperature, ice composition, and morphology are reported. This work also points out the IR features that are considered the best promising tracers when searching for interstellar acetone-containing ices. Methods. Acetone-containing ices were grown at 15 K under high-vacuum conditions and infrared (IR) spectra (500–4000 cm−1/20–2.5 μm, 0.5 cm−1 resolution) in transmission mode were recorded using a Fourier transform infrared spectrometer. Spectra of the ices at higher temperatures are acquired during the heating of the sample (at a rate of 25 K h−1) up to 160 K. The changes in the infrared features for varying conditions were analyzed. Results. A large set of IR spectra of acetone-containing ices is presented and made available as a basis for interpreting current and future infrared astronomical spectra. The peak position and full width at half maximum of selected acetone bands have been measured for different ice mixtures and temperatures. The bands that are best suitable for acetone identification in astronomical spectra are: the C=O stretch mode, around 1710.3 cm−1 (5.847 μm), that lies in the 1715–1695 cm−1 (5.83–5.90 μm) range in the mixed ices; the CH3 symmetric deformation, around 1363.4 cm−1 (7.335 μm) that lies in the 1353–1373 cm−1 (7.28–7.39 μm) range in the mixed ices; and the CCC asymmetric stretch, around 1228.4 cm−1 (8.141 μm), that lies in the 1224–1245 cm−1 (8.16–8.03 μm) range in the mixed ices. The CCC asymmetric stretch band also exhibits potential as a remote probe of the ice temperature and composition; this feature is the superposition of two components that respond differently to temperature and the presence of CH3OH. All the spectra are available through the Leiden Ice Database.
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46

Vinogradoff, V., F. Duvernay, N. Fray, M. Bouilloud, T. Chiavassa, and H. Cottin. "CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS." Astrophysical Journal 809, no. 2 (August 13, 2015): L18. http://dx.doi.org/10.1088/2041-8205/809/2/l18.

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47

Rachid, Marina G., Jeroen Terwisscha van Scheltinga, Daniël Koletzki, Giulia Marcandalli, Ewine F. van Dishoeck, and Harold Linnartz. "Laboratory data in support of JWST observations of interstellar ices." Proceedings of the International Astronomical Union 15, S350 (April 2019): 420–21. http://dx.doi.org/10.1017/s1743921319009827.

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AbstractExperimental and theoretical studies have shown that Complex Organic Molecules (COMs) can be formed on icy dusty grains in molecular clouds and protoplanetary disks. The number of astronomical detections of solid COMs, however, is very limited. With the upcoming launch of the James Webb Space Telescope (JWST) this should change, but in order to identify solid state features of COMs, accurate laboratory data are needed. Here we present high resolution (0.5 cm–1) infrared ice spectra of acetone (C3H6O) and methyl formate (HCOOCH3), two molecules already identified in astronomical gas phase surveys, whose interstellar synthesis is expected to follow solid state pathways.
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48

Hu, Xiaoyi, Yuanyuan Yang, Congcong Zhang, Yang Chen, Junfeng Zhen, and Liping Qin. "Gas-phase laboratory formation of large, astronomically relevant PAH-organic molecule clusters." Astronomy & Astrophysics 656 (December 2021): A80. http://dx.doi.org/10.1051/0004-6361/202141407.

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Polycyclic aromatic hydrocarbon (PAH) molecules may play an essential role in the prebiotic compound evolution network in interstellar clouds. In this work, an experimental study of large, astronomically relevant PAH-organic molecule clusters is presented. With the initial molecular precursors dicoronylene (DC; C48H20)-pyroglutamic acid (Pga, C5H7NO3), DC-proline (Pro; C5H9NO2), and DC-pyroglutaminol (Pgn; C5H9NO2), our experiments indicate that PAH–organic molecule cluster cations (e.g., (Pga)(1−2)C48Hn+, (Pro)(1−2)C48Hn+, and (Pgn)(1−6)C48Hn+) and carbon cluster–organic molecule cluster cations (e.g., (Pga)C48+, (Pro)(1−2)C48+, and (Pgn)(1−6)C48+) are gradually formed through an ion-molecule collision reaction pathway in the presence of a strong galactic interstellar radiation field. These laboratory studies provide a gas-phase growth route toward the formation of complex prebiotic compounds in a bottom-up growth process, as well as insight into their chemical-evolution behavior in the interstellar medium.
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49

Chuang, K. J. "Solid-state production of complex organic molecules: H-atom addition versus UV irradiation." Proceedings of the International Astronomical Union 13, S332 (March 2017): 429–34. http://dx.doi.org/10.1017/s1743921317007888.

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AbstractComplex organic molecules (COMs) have been observed in comets, hot cores and cold dense regions of the interstellar medium. It is generally accepted that these COMs form on icy dust grain through the recombination reaction of radicals triggered by either energetic UV-photon or non-energetic H-atom addition processing. In this work, we present for the first time laboratory studies that allow for quantitative comparison of hydrogenation and UV-induced reactions as well as their cumulative effect in astronomically relevant CO:CH3OH=4:1 ice analogues. The formation of glycolaldehyde (GA) and ethylene glycol (EG) is confirmed in pure hydrogenation experiments at 14 K, except methyl formate (MF), which is only clearly observed in photolysis. The fractions for MF:GA:EG are 0 : (0.2-0.4) : (0.8-0.6) for pure hydrogenation, and 0.2 : 0.3 : 0.5 for UV involving experiments and can offer a diagnostic tool to derive the chemical origin of these species. The GA/EG ratios in the laboratory (0.3-1.5) compare well with observations toward different objects.
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50

Cruikshank, D. P. "Complex Organic Solid Matter in the Outer Solar System." Highlights of Astronomy 13 (2005): 902–3. http://dx.doi.org/10.1017/s1539299600017482.

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Complex organic molecular material of non-biological origin is found in abundance in the interstellar dust in our Galaxy, and is also detected in other galaxies. Some of this material was incorporated into the solar nebula and is now found in some Solar System bodies. While some pre-solar organic material has been preserved, synthesis of complex organics in planetary atmospheres and on icy surfaces has been in progress for the entire age of the Solar System. Refractory organic solids have proven difficult to detect by traditional spectroscopic techniques, and their presence is usually inferred from the low albedo and (often) red color of the surfaces of small bodies in the outer Solar System (OSS). Color in complex organic molecules, such as polymers and polycyclic aromatic hydrocarbons, is caused by absorption in the UV and visible spectral regions arising from electronic transitions connected primarily with C-C and C-0 bonding. In particular, large hydrocarbon molecules with conjugated (alternating pairs of double and single) C-C bonds have color because the electronic transitions of the de-localized pi electrons extend into the visible spectral region; the longer the conjugated chain, the further is the extension to longer wavelength, with the result that especially large molecular material appears black.
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