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Brigiano, Flavio Siro, Yannick Jeanvoine, Antonio Largo i Riccardo Spezia. "The formation of urea in space". Astronomy & Astrophysics 610 (luty 2018): A26. http://dx.doi.org/10.1051/0004-6361/201731610.
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Context. Many organic molecules have been observed in the interstellar medium thanks to advances in radioastronomy, and very recently the presence of urea was also suggested. While those molecules were observed, it is not clear what the mechanisms responsible to their formation are. In fact, if gas-phase reactions are responsible, they should occur through barrierless mechanisms (or with very low barriers). In the past, mechanisms for the formation of different organic molecules were studied, providing only in a few cases energetic conditions favorable to a synthesis at very low temperature. A particularly intriguing class of such molecules are those containing one N–C–O peptide bond, which could be a building block for the formation of biological molecules. Urea is a particular case because two nitrogen atoms are linked to the C–O moiety. Thus, motivated also by the recent tentative observation of urea, we have considered the synthetic pathways responsible to its formation. Aims. We have studied the possibility of forming urea in the gas phase via different kinds of bi-molecular reactions: ion-molecule, neutral, and radical. In particular we have focused on the activation energy of these reactions in order to find possible reactants that could be responsible for to barrierless (or very low energy) pathways. Methods. We have used very accurate, highly correlated quantum chemistry calculations to locate and characterize the reaction pathways in terms of minima and transition states connecting reactants to products. Results. Most of the reactions considered have an activation energy that is too high; but the ion-molecule reaction between NH2OHNH2OH2+ and formamide is not too high. These reactants could be responsible not only for the formation of urea but also of isocyanic acid, which is an organic molecule also observed in the interstellar medium.
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West, Niclas A., Edward Rutter, Mark A. Blitz, Leen Decin i Dwayne E. Heard. "Low temperature gas phase reaction rate coefficient measurements: Toward modeling of stellar winds and the interstellar medium". Proceedings of the International Astronomical Union 15, S350 (kwiecień 2019): 382–83. http://dx.doi.org/10.1017/s1743921319007531.
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AbstractStellar winds of Asymptotic Giant Branch (AGB) stars are responsible for the production of ∼85% of the gas molecules in the interstellar medium (ISM), and yet very few of the gas phase rate coefficients under the relevant conditions (10 – 3000 K) needed to model the rate of production and loss of these molecules in stellar winds have been experimentally measured. If measured at all, the value of the rate coefficient has often only been obtained at room temperature, with extrapolation to lower and higher temperatures using the Arrhenius equation. However, non-Arrhenius behavior has been observed often in the few measured rate coefficients at low temperatures. In previous reactions studied, theoretical simulations of the formation of long-lived pre-reaction complexes and quantum mechanical tunneling through the barrier to reaction have been utilized to fit these non-Arrhenius behaviours of rate coefficients.Reaction rate coefficients that were predicted to produce the largest change in the production/loss of Complex Organic Molecules (COMs) in stellar winds at low temperatures were selected from a sensitivity analysis. Here we present measurements of rate coefficients using a pulsed Laval nozzle apparatus with the Pump Laser Photolysis - Laser Induced Fluorescence (PLP-LIF) technique. Gas flow temperatures between 30 – 134 K have been produced by the University of Leeds apparatus through the controlled expansion of N2 or Ar gas through Laval nozzles of a range of Mach numbers between 2.49 and 4.25.Reactions of interest include those of OH, CN, and CH with volatile organic species, in particular formaldehyde, a molecule which has been detected in the ISM. Kinetics measurements of these reactions at low temperatures will be presented using the decay of the radical reagent. Since formaldehyde and the formal radical (HCO) are potential building blocks of COMs in the interstellar medium, low temperature reaction rate coefficients for their production and loss can help to predict the formation pathways of COMs observed in the interstellar medium.
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Parker, Dorian S. N., Ralf I. Kaiser, Oleg Kostko, Tyler P. Troy, Musahid Ahmed, Bing-Jian Sun, Shih-Hua Chen i A. H. H. Chang. "On the formation of pyridine in the interstellar medium". Physical Chemistry Chemical Physics 17, nr 47 (2015): 32000–32008. http://dx.doi.org/10.1039/c5cp02960k.
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The nitrogen bearing aromatic molecule pyridine (C5H5N) is revealed to form in high temperature environments simulating conditions in carbon-rich circumstellar envelopes via the reaction of the cyano vinyl radical with vinyl cyanide.
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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 (kwiecień 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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Miksch, April M., Annalena Riffelt, Ricardo Oliveira, Johannes Kästner i Germán Molpeceres. "Hydrogenation of small aromatic heterocycles at low temperatures". Monthly Notices of the Royal Astronomical Society 505, nr 3 (27.05.2021): 3157–64. http://dx.doi.org/10.1093/mnras/stab1514.
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ABSTRACT The recent wave of detections of interstellar aromatic molecules has sparked interest in the chemical behaviour of aromatic molecules under astrophysical conditions. In most cases, these detections have been made through chemically related molecules, called proxies, that implicitly indicate the presence of a parent molecule. In this study, we present the results of the theoretical evaluation of the hydrogenation reactions of different aromatic molecules (benzene, pyridine, pyrrole, furan, thiophene, silabenzene, and phosphorine). The viability of these reactions allows us to evaluate the resilience of these molecules to the most important reducing agent in the interstellar medium, the hydrogen atom (H). All significant reactions are exothermic and most of them present activation barriers, which are, in several cases, overcome by quantum tunnelling. Instanton reaction rate constants are provided between 50 and 500 K. For the most efficiently formed radicals, a second hydrogenation step has been studied. We propose that hydrogenated derivatives of furan and pyrrole, especially 2,3-dihydropyrrole, 2,5-dihydropyrrole, 2,3-dihydrofuran, and 2,5-dihydrofuran, are promising candidates for future interstellar detections.
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Doddipatla, Srinivas, Galiya R. Galimova, Hongji Wei, Aaron M. Thomas, Chao He, Zhenghai Yang, Alexander N. Morozov, Christopher N. Shingledecker, Alexander M. Mebel i Ralf I. Kaiser. "Low-temperature gas-phase formation of indene in the interstellar medium". Science Advances 7, nr 1 (styczeń 2021): eabd4044. http://dx.doi.org/10.1126/sciadv.abd4044.
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Polycyclic aromatic hydrocarbons (PAHs) are fundamental molecular building blocks of fullerenes and carbonaceous nanostructures in the interstellar medium and in combustion systems. However, an understanding of the formation of aromatic molecules carrying five-membered rings—the essential building block of nonplanar PAHs—is still in its infancy. Exploiting crossed molecular beam experiments augmented by electronic structure calculations and astrochemical modeling, we reveal an unusual pathway leading to the formation of indene (C9H8)—the prototype aromatic molecule with a five-membered ring—via a barrierless bimolecular reaction involving the simplest organic radical—methylidyne (CH)—and styrene (C6H5C2H3) through the hitherto elusive methylidyne addition–cyclization–aromatization (MACA) mechanism. Through extensive structural reorganization of the carbon backbone, the incorporation of a five-membered ring may eventually lead to three-dimensional PAHs such as corannulene (C20H10) along with fullerenes (C60, C70), thus offering a new concept on the low-temperature chemistry of carbon in our galaxy.
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Zaverkin, V., T. Lamberts, M. N. Markmeyer i J. Kästner. "Tunnelling dominates the reactions of hydrogen atoms with unsaturated alcohols and aldehydes in the dense medium". Astronomy & Astrophysics 617 (wrzesień 2018): A25. http://dx.doi.org/10.1051/0004-6361/201833346.
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Hydrogen addition and abstraction reactions play an important role as surface reactions in the buildup of complex organic molecules in the dense interstellar medium. Addition reactions allow unsaturated bonds to be fully hydrogenated, while abstraction reactions recreate radicals that may undergo radical–radical recombination reactions. Previous experimental work has indicated that double and triple C–C bonds are easily hydrogenated, but aldehyde –C=O bonds are not. Here, we investigate a total of 29 reactions of the hydrogen atom with propynal, propargyl alcohol, propenal, allyl alcohol, and propanal by means of quantum chemical methods to quantify the reaction rate constants involved. First of all, our results are in good agreement with and can explain the observed experimental findings. The hydrogen addition to the aldehyde group, either on the C or O side, is indeed slow for all molecules considered. Abstraction of the H atom from the aldehyde group, on the other hand, is among the faster reactions. Furthermore, hydrogen addition to C–C double bonds is generally faster than to triple bonds. In both cases, addition on the terminal carbon atom that is not connected to other functional groups is easiest. Finally, we wish to stress that it is not possible to predict rate constants based solely on the type of reaction: the specific functional groups attached to a backbone play a crucial role and can lead to a spread of several orders of magnitude in the rate constant.
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Ferrero, Stefano, Cecilia Ceccarelli, Piero Ugliengo, Mariona Sodupe i Albert Rimola. "Formation of Complex Organic Molecules on Interstellar CO Ices? Insights from Computational Chemistry Simulations". Astrophysical Journal 951, nr 2 (1.07.2023): 150. http://dx.doi.org/10.3847/1538-4357/acd192.
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Abstract The carbon (3P) atom is a reactive species that, according to laboratory experiments and theoretical calculations, condensates with interstellar ice components. This fact is of uttermost importance for the chemistry in the interstellar medium (ISM) because the condensation reaction is barrierless, and the subsequent species formed are still reactive given their open-shell character. Carbon condensation on CO-rich ices forms the C=C=O (3Σ−) species, which can be easily hydrogenated twice to form ketene (H2CCO). Ketene is very reactive in terrestrial conditions, usually found as an intermediate that is difficult to isolate in chemical synthesis laboratories. These characteristics suggest that ketene can be a good candidate to form interstellar complex organic molecules via a two-step process, i.e., its activation followed by a radical–radical coupling. In this work, reactions between ketene and atomic H and the OH and NH2 radicals on a CO-rich ice model have been explored by means of quantum chemical calculations complemented by kinetic calculations to evaluate if they are favorable in the ISM. Results indicate that the addition of H to ketene (helped by tunneling) to form the acetyl radical (CH3CO) is the most preferred path as the reactions with OH and NH2 possess activation energies (≥9 kJ mol−1) hard to surmount in the ISM conditions unless external processes provide energy to the system. Thus, acetaldehyde (CH3CHO) and, probably, ethanol (CH3CH2OH) formation via further hydrogenations, are the possible unique operating synthetic routes. Moreover, from the computed, relatively large binding energies of OH and NH2 on CO ice, slow diffusion is expected, hampering possible radical–radical couplings with CH3CO. The astrophysical implications of these findings are discussed considering the incoming James Webb Space Telescope observations.
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Lu, Shiru, Zhisen Meng, Peng Xie, Enwei Liang i Zhao Wang. "Gas-phase formation of interstellar nucleobases from dehydrogenated formamide and vinyl cyanide". Astronomy & Astrophysics 656 (grudzień 2021): A84. http://dx.doi.org/10.1051/0004-6361/202140744.
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Context. Cytosine, thymine, and uracil are three of the five primary nucleobases that function as the fundamental units of the genetic code in nucleic acids. In searching the extraterrestrial origins of microscopic life, previous studies have reported formation routes of nucleobases in interstellar ice analogs. The present work explores the possibility that nucleobases could form from small molecules through gas-phase reactions in the interstellar medium (ISM). Aims. We aim to search energetically favorable synthetic routes toward the formation of cytosine, thymine, and uracil via gas-phase reactions, using first principles calculations. Based on the computation of a reaction energy barrier and reactant formation energy, we tried to identify the specific interstellar environments favorable to the formation of the nucleobases, with respect to the previously reported detection of relevant reactants in the ISM. Methods. Density functional theory calculations were carried out to investigate the chemical reaction pathways using the M06 functional with 6-31+G(d,p)/6-311++G(d,p) basis sets. An ab initio Møller-Plesset perturbation theory in the second order (MP2) was also used to corroborate the results. Results. We report synthetic routes toward the formation of cytosine, thymine, and uracil through gas-phase reactions between partially dehydrogenated formamide (H2NCHO) and vinyl cyanide (H2CCHCN). The most energetically favorable pathway to the formation of 1H-pyrimidin-2-one (C4H4N2O), a direct precursor of nucleobases, was found in a molecule-radical reaction between HNCHO and H2CCHCN, with an energy barrier of 19.3 kcal mol−1. The energy barriers for the optimal reaction pathways between C4H4N2O and amino, methyl, or hydroxyl to finally produce cytosine, thymine, or uracil are about 11.3, 18.6, or 19.9 kcal mol−1, respectively. Conclusions. The optimal energy barriers of 19.3 and 23.8 kcal mol−1 roughly correspond to a reaction rate coefficient of 10−11 cm3 s−1 at 180 and 220 K, respectively. This indicates that the reaction could be thermally feasible through a gas-phase reaction in hot molecular cores or in the inner part of the protoplanetary disks. In contrast, the energy barriers for the reactions between other dehydrogenated radicals and molecules are relatively high, which corresponds to the extinction energy of far-ultraviolet photons in photo-dissociation regions. Furthermore, the computed pathways suggest that prior H migration in the reactants could be the key rate-determining process for the synthesis of the primary nucleobases.
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Inostroza, Natalia, Diego Mardones, Jose Cernicharo, Hans Zinnecker, Jixing Ge, Nelson Aria, Patricio Fuentealba i Carlos Cardenas. "Formation of complex organic molecules in ice mantles: An ab initio molecular dynamics study". Astronomy & Astrophysics 629 (30.08.2019): A28. http://dx.doi.org/10.1051/0004-6361/201834035.
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We present a detailed simulation of a dust grain covered by a decamer of (CH3OH)10-ice-mantle, bombarded by an OH− closed-shell molecule with kinetic energies from 10–22 eV. The chemical pathways are studied through Born-Oppenheimer (ab initio) molecular dynamics. The simulations show that methanol ice-mantles can be a key generator of complex organic molecules (COMs). We report the formation of COMs such as methylene glycol (CH2(OH)2) and the OCH2OH radical, which have not been detected yet in the interstellar medium (ISM). We discuss the chemical formation of new species through the reaction of CH3OH with the hydroxyl projectile. The dependence of the outcome on the kinetic energy of the projectile and the implications for the observation and detection of these molecules might explain why the methoxy radical (CH3 ⋅ ) has been observed in a wider range of astrophysical environments than the hydroxymethyl (CH2OH ⋅) isomer. Because of the projectile kinetic energies required for these reactions to occur, we suggest that these processes are likely relevant in the production of COMs in photodissociation and shock regions produced by high-velocity jets and outflows from young stellar objects.
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Kaiser, Ralf I., i Nadia Balucani. "Astrobiology – the final frontier in chemical reaction dynamics". International Journal of Astrobiology 1, nr 1 (styczeń 2002): 15–23. http://dx.doi.org/10.1017/s1473550402001015.
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Crossed-beam experiments on the reactions of cyano CN(X2Σ+) and ethinyl C2H(X2Σ+) radicals with the unsaturated hydrocarbons acetylene, ethylene, methylacetylene allene and benzene have been carried out under single-collision conditions to investigate synthetic routes to form nitriles, polyynes and substituted allenes in hydrocarbon-rich atmospheres of planets and their moons. All reactions were found to proceed without an entrance barrier, to have exit barriers well below the energy of the reactant molecules and to be strongly exothermic. The predominant identification of the radical versus atomic hydrogen exchange channel makes these reactions compelling candidates for the formation of complex organic chemicals – precursors to biologically important amino acids – in Solar system environments and in the interstellar medium.
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Puzzarini, Cristina, Zoi Salta, Nicola Tasinato, Jacopo Lupi, Carlo Cavallotti i 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, nr 4 (16.06.2020): 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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Rivilla, Víctor M., Laura Colzi, Izaskun Jiménez-Serra, Jesús Martín-Pintado, Andrés Megías, Mattia Melosso, Luca Bizzocchi i in. "Precursors of the RNA World in Space: Detection of (Z)-1,2-ethenediol in the Interstellar Medium, a Key Intermediate in Sugar Formation". Astrophysical Journal Letters 929, nr 1 (1.04.2022): L11. http://dx.doi.org/10.3847/2041-8213/ac6186.
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Abstract We present the first detection of (Z)-1,2-ethenediol, (CHOH)2, the enol form of glycolaldehyde, in the interstellar medium toward the G+0.693−0.027 molecular cloud located in the Galactic Center. We have derived a column density of (1.8 ± 0.1) × 1013 cm−2, which translates into a molecular abundance with respect to molecular hydrogen of 1.3 × 10−10. The abundance ratio between glycolaldehyde and (Z)-1,2-ethenediol is ∼5.2. We discuss several viable formation routes through chemical reactions from precursors such as HCO, H2CO, CHOH, or CH2CHOH. We also propose that this species might be an important precursor in the formation of glyceraldehyde (HOCH2CHOHCHO) in the interstellar medium through combination with the hydroxymethylene (CHOH) radical.
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Leroux, Killian, i Lahouari Krim. "Thermal and photochemical study of CH3OH and CH3OH–O2 astrophysical ices". Monthly Notices of the Royal Astronomical Society 500, nr 1 (20.10.2020): 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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Bacmann, A., A. Faure, P. Hily-Blant, K. Kobayashi, H. Ozeki, S. Yamamoto, L. Pagani i F. Lique. "Deuterium fractionation of nitrogen hydrides: detections of NHD and ND2". Monthly Notices of the Royal Astronomical Society 499, nr 2 (23.09.2020): 1795–804. http://dx.doi.org/10.1093/mnras/staa2903.
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ABSTRACT Although ammonia is an abundant molecule commonly observed towards the dense interstellar medium, it has not yet been established whether its main formation route is from gas-phase ion–molecule reactions or grain-surface hydrogen additions on adsorbed nitrogen atoms. Deuterium fractionation can be used as a tool to constrain formation mechanisms. High abundances of deuterated molecules are routinely observed in the dense interstellar medium, with the ratio between deuterated molecules and the main isotopologue enhanced by several orders of magnitude with respect to the elemental D/H ratio. In the case of ammonia, the detection of its triply deuterated isotopologue hints at high abundances of the deuterated intermediate nitrogen radicals, ND, NHD, and ND2. So far however, only ND has been detected in the interstellar medium. In this paper, to constrain the formation of ammonia, we aim at determining the NHD/NH2 and ND2/NHD abundance ratios, and compare them with the predictions of both pure gas-phase and grain-surface chemical models. We searched for the fundamental rotational transitions of NHD and ND2 towards the class 0 protostar IRAS16293−2422, towards which NH, NH2 and ND had been previously detected. Both NHD and ND2 are detected in absorption towards the source. The relative abundance ratios NH2:NHD:ND2 are close to 8:4:1. These ratios can be reproduced by our gas-phase chemical model within a factor of 2–3. Statistical ratios as expected from grain-surface chemistry are also consistent with our data. Further investigations of the ortho-to-para ratio in ND2 , both theoretical and observational, could bring new constraints to better understand nitrogen hydride chemistry.
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Redondo, P., F. Pauzat, Y. Ellinger i A. Markovits. "Reconstruction of water ice: the neglected process OH + OH → H2O + O". Astronomy & Astrophysics 638 (czerwiec 2020): A125. http://dx.doi.org/10.1051/0004-6361/202037771.
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Context. Although H2O is the most important molecular material found in the solid state in the interstellar medium, the chemical routes leading to ice through surface reactions are still a matter of discussion. Three reaction pathways proposed in the past are at the heart of current research: hydrogenation of atomic oxygen, molecular oxygen, and ozone. The reaction network finally leads to a small number of processes giving H2O: H + OH, H2 + OH, and H + H2O2. To these processes, OH + OH should be added. It is known to be efficient in atmospheric chemistry and takes the irradiations of the interstellar grains into account that, directly or indirectly, create a number of OH radicals on and in the icy mantles. Aims. We study the role of the existing ice in its own reconstruction after it is destroyed by the constant irradiation of interstellar grains and focus on the OH + OH reaction in the triplet state. Methods. We used numerical simulations with a high level of coupled cluster ab initio calculations for small water aggregates and methods relevant to density functional theory for extended systems, including a periodic description in the case of solid water of infinite dimensions. Results. OH + OH → H2O + O reaction profiles are reported that take the involvement of an increasing number of H2O support molecules into account. It is found that the top of the barrier opposing the reaction gradually decreases with the number of supporting H2O and falls below the level of the reactants for H2O layers or solid water. Conclusions. In contrast to the gas phase, the reaction is barrierless on water ice. By adding a reconstructed H2O molecule and a free oxygen atom at the surface of the remaining ice, this reaction leaves open the possibility of the ice reconstruction.
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Cuppen, H. M., i A. Fredon. "Simulations of energy dissipation and non-thermal desorption on amorphous solid water". Proceedings of the International Astronomical Union 15, S350 (kwiecień 2019): 81–85. http://dx.doi.org/10.1017/s1743921320000861.
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AbstractDust particles covered by icy mantles play a crucial role in the formation of molecules in the Interstellar Medium (ISM). These icy mantles are mainly composed of water but many other chemical species are also contained in these ices. These compounds can diffuse and meet each other to react. It is through these surface reactions that new saturated species are formed. Photodissociation reactions are also thought to play a crucial role in the formation of radical species. Complex organic molecules are formed through an intricated network of photodissociation and surface reactions.Both type of reactions release energy. Surface reactions are typically exothermic by a few eV, whereas photodissociation reactions are triggered by the absorption of a UV photon, resulting in the formation of highly excited products. The excited reaction products can apply this energy for desorption or diffusion, making products more mobile than predicted when considering only thermal hopping. The energy could further lead to annealing or deformation of the ice structure.Here we would like to quantify the relative importance of these different energy dissipation routes. For this we performed thousands of Molecular Dynamics simulations for three different species (CO2, H2O and CH4) on top of a water ice surface. We consider different types of excitation such as translational, rotational, and/or vibrational excitation. The applied substrate is an amorphous solid water surface (ASW).
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Rivilla, Víctor M., Miguel Sanz-Novo, Izaskun Jiménez-Serra, Jesús Martín-Pintado, Laura Colzi, Shaoshan Zeng, Andrés Megías i in. "First Glycine Isomer Detected in the Interstellar Medium: Glycolamide (NH2C(O)CH2OH)". Astrophysical Journal Letters 953, nr 2 (1.08.2023): L20. http://dx.doi.org/10.3847/2041-8213/ace977.
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Abstract We report the first detection in the interstellar medium (ISM) of a C2H5O2N isomer: syn-glycolamide (NH2C(O)CH2OH). The exquisite sensitivity at sub-mK levels of an ultradeep spectral survey carried out with the Yebes 40 m and IRAM 30 m telescopes toward the G+0.693–0.027 molecular cloud has allowed us to unambiguously identify multiple transitions of this species. We derived a column density of (7.4 ± 0.7) × 1012 cm−2, which implies a molecular abundance with respect to H2 of 5.5 × 10−11. The other C2H5O2N isomers, including the higher-energy anti conformer of glycolamide and two conformers of glycine, were not detected. The upper limit derived for the abundance of glycine indicates that this amino acid is surely less abundant than its isomer glycolamide in the ISM. The abundances of the C2H5O2N isomers cannot be explained in terms of thermodynamic equilibrium; thus, chemical kinetics need to be invoked. While the low abundance of glycine might not be surprising, based on the relative low abundances of acids in the ISM compared to other compounds (e.g., alcohols, aldehydes, or amines), several chemical pathways can favor the formation of its isomer glycolamide. It can be formed through radical–radical reactions on the surface of dust grains. The abundances of these radicals can be significantly boosted in an environment affected by a strong ultraviolet field induced by cosmic rays, such as that expected in G+0.693–0.027. Therefore, as shown by several recent molecular detections toward this molecular cloud, it stands out as the best target to discover new species with carbon, oxygen, and nitrogen with increasing chemical complexity.
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Leroux, Killian, Jean-Claude Guillemin i Lahouari Krim. "Hydrogenation of glycolaldehyde to ethylene glycol at 10 K". Monthly Notices of the Royal Astronomical Society 507, nr 2 (9.08.2021): 2632–42. http://dx.doi.org/10.1093/mnras/stab2267.
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ABSTRACT Glycolaldehyde, the simplest sugar, is a complex organic molecule detected in many regions of the interstellar medium (ISM). Although its synthetic routes are fairly well known and consistent with many laboratory studies, queries still arise about its reactivity and its role in the complex chemistry of the ISM. This study shows the surface and bulk hydrogenation of glycolaldehyde at 10 K in order to confirm or invalidate the astrophysical models which suggest that CHOCH2OH would be a precursor of ethylene glycol through hydrogenation processes occurring on the surface of interstellar dust grains. By coupling IR spectroscopy and mass spectrometry, we show that the formation of HOCH2CH2OH from CHOCH2OH + H solid state reaction occurs, supporting the existence of a chemical link between these two organics in the ISM. This work suggests that while CHO + CH2OH and CH2OH + CH2OH radical recombination would lead to CHOCH2OH and HOCH2CH2OH, respectively, the presence of H-atoms in the ISM would be a secondary source to favour ethylene glycol over glycolaldehyde. These results are in good agreement with different astronomical observations which show simultaneous detections of glycolaldehyde and ethylene glycol with an abundance ratio HOCH2CH2OH/CHOCH2OH ranged between 1 and 15.
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He, Chao, Galiya R. Galimova, Yuheng Luo, Long Zhao, André K. Eckhardt, Rui Sun, Alexander M. Mebel i Ralf I. Kaiser. "A chemical dynamics study on the gas-phase formation of triplet and singlet C5H2carbenes". Proceedings of the National Academy of Sciences 117, nr 48 (16.11.2020): 30142–50. http://dx.doi.org/10.1073/pnas.2019257117.
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Since the postulation of carbenes by Buchner (1903) and Staudinger (1912) as electron-deficient transient species carrying a divalent carbon atom, carbenes have emerged as key reactive intermediates in organic synthesis and in molecular mass growth processes leading eventually to carbonaceous nanostructures in the interstellar medium and in combustion systems. Contemplating the short lifetimes of these transient molecules and their tendency for dimerization, free carbenes represent one of the foremost obscured classes of organic reactive intermediates. Here, we afford an exceptional glance into the fundamentally unknown gas-phase chemistry of preparing two prototype carbenes with distinct multiplicities—triplet pentadiynylidene (HCCCCCH) and singlet ethynylcyclopropenylidene (c-C5H2) carbene—via the elementary reaction of the simplest organic radical—methylidyne (CH)—with diacetylene (HCCCCH) under single-collision conditions. Our combination of crossed molecular beam data with electronic structure calculations and quasi-classical trajectory simulations reveals fundamental reaction mechanisms and facilitates an intimate understanding of bond-breaking processes and isomerization processes of highly reactive hydrocarbon intermediates. The agreement between experimental chemical dynamics studies under single-collision conditions and the outcome of trajectory simulations discloses that molecular beam studies merged with dynamics simulations have advanced to such a level that polyatomic reactions with relevance to extreme astrochemical and combustion chemistry conditions can be elucidated at the molecular level and expanded to higher-order homolog carbenes such as butadiynylcyclopropenylidene and triplet heptatriynylidene, thus offering a versatile strategy to explore the exotic chemistry of novel higher-order carbenes in the gas phase.
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Robert, François, Sylvie Derenne, Guillaume Lombardi, Khaled Hassouni, Armelle Michau, Peter Reinhardt, Rémi Duhamel, Adriana Gonzalez i Kasia Biron. "Hydrogen isotope fractionation in methane plasma". Proceedings of the National Academy of Sciences 114, nr 5 (17.01.2017): 870–74. http://dx.doi.org/10.1073/pnas.1615767114.
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The hydrogen isotope ratio (D/H) is commonly used to reconstruct the chemical processes at the origin of water and organic compounds in the early solar system. On the one hand, the large enrichments in deuterium of the insoluble organic matter (IOM) isolated from the carbonaceous meteorites are interpreted as a heritage of the interstellar medium or resulting from ion−molecule reactions taking place in the diffuse part of the protosolar nebula. On the other hand, the molecular structure of this IOM suggests that organic radicals have played a central role in a gas-phase organosynthesis. So as to reproduce this type of chemistry between organic radicals, experiments based on a microwave plasma of CH4have been performed. They yielded a black organic residue in which ion microprobe analyses revealed hydrogen isotopic anomalies at a submicrometric spatial resolution. They likely reflect differences in the D/H ratios between the various CHxradicals whose polymerization is at the origin of the IOM. These isotopic heterogeneities, usually referred to as hot and cold spots, are commensurable with those observed in meteorite IOM. As a consequence, the appearance of organic radicals in the ionized regions of the disk surrounding the Sun during its formation may have triggered the formation of organic compounds.
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Rawlings, J. M. C., D. A. Williams, S. Viti, C. Cecchi-Pestellini i 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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Ocaña, Antonio J., Sergio Blázquez, Daniel González, Alexey Potapov, Bernabé Ballesteros, André Canosa, María Antiñolo, José Albaladejo i Elena Jiménez. "Gas-phase reactivity of CH3OH+OH down to 11.7 K: Astrophysical implications". Proceedings of the International Astronomical Union 15, S350 (kwiecień 2019): 365–67. http://dx.doi.org/10.1017/s1743921319007579.
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AbstractMethanol (CH3OH) and hydroxyl (OH) radicals are two species abundant in cold and dense molecular clouds which are important for the chemistry of the interstellar medium (ISM). CH3OH is a well-known starting point for the formation of more complex organic molecules (COMs) in these molecular clouds. Thus, the reactivity of CH3OH in the gas-phase with OH may play a crucial role in the formation of species as complex as prebiotic molecules in the ISM and reliable rate coefficients should be used in astrochemical models describing low temperature reaction networks.
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Singh, Santosh K., N. Fabian Kleimeier, André K. Eckhardt i Ralf I. Kaiser. "A Mechanistic Study on the Formation of Acetone (CH3COCH3), Propanal (CH3CH2CHO), Propylene Oxide (c-CH3CHOCH2) along with Their Propenol Enols (CH3CHCHOH/CH3C(OH)CH2) in Interstellar Analog Ices". Astrophysical Journal 941, nr 2 (1.12.2022): 103. http://dx.doi.org/10.3847/1538-4357/ac8c92.
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Abstract Carbonyl-bearing complex organic molecules (COMs) in the interstellar medium (ISM) are of significant importance due to their role as potential precursors to biomolecules. Simple aldehydes and ketones like acetaldehyde, acetone, and propanal have been recognized as fundamental molecular building blocks and tracers of chemical processes involved in the formation of distinct COMs in molecular clouds and star-forming regions. Although previous laboratory simulation experiments and modeling established the potential formation pathways of interstellar acetaldehyde and propanal, the underlying formation routes to the simplest ketone—acetone—in the ISM are still elusive. Herein, we performed a systematic study to unravel the synthesis of acetone, its propanal and propylene oxide isomers, as well as the propenol tautomers in interstellar analog ices composed of methane and acetaldehyde along with isotopic-substitution studies to trace the reaction pathways of the reactive intermediates. Chemical processes in the ices were triggered at 5.0 K upon exposure to proxies of Galactic cosmic rays in the form of energetic electrons. The products were detected isomer-selectively via vacuum ultraviolet (VUV) photoionization reflectron time-of-flight mass spectrometry. In our experiments, the branching ratio of acetone (CH3COCH3):propylene oxide (c-CH3CHOCH2):propanal (CH3CH2CHO) was determined to be (4.82 ± 0.05):(2.86 ± 0.13):1. The radical–radical recombination reaction leading to acetone emerged as the dominant channel. The propenols appeared only at a higher radiation dose via keto–enol tautomerization. The current study provides mechanistic information on the fundamental nonequilibrium pathways that may be responsible for the formation of acetone and its (enol) isomers inside the interstellar icy grains.
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Slate, Eren C. S., Rory Barker, Ryan T. Euesden, Max R. Revels i Anthony J. H. M. Meijer. "Computational studies into urea formation in the interstellar medium". Monthly Notices of the Royal Astronomical Society 497, nr 4 (14.08.2020): 5413–20. http://dx.doi.org/10.1093/mnras/staa2436.
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ABSTRACT Formation routes, involving closed shell, radical, and charged species for urea, have been studied using computational methods to probe their feasibility in the interstellar medium. All reactions involving closed shell species were found to have prohibitive barriers. The radical–radical reaction possesses a barrier of only 4 kJ mol−1, which could be surmountable. A charged species based route was also investigated. A barrier of only 8 kJ mol−1 was found in that case, when a partial water ice shell was included.
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Leroux, Killian, Jean-Claude Guillemin i Lahouari Krim. "Organic residues in astrophysical ice analogues: Thermal processing of hydrogenated glyoxal ices under interstellar conditions". Monthly Notices of the Royal Astronomical Society 504, nr 2 (14.04.2021): 2181–89. http://dx.doi.org/10.1093/mnras/stab951.
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ABSTRACT Organic residues are considered as part of the chemical composition of the interstellar dust grains. They are formed under the extreme conditions of the interstellar medium and play an important role in exobiology. They may contain pre-biotic organic species such as amino acids, constituents of proteins and building blocks of DNA and RNA, key elements of life. By investigating the formation of organic residues in an astrophysical context, many groups have been focusing in the UV irradiation and subsequent warm-up of astrophysical ice analogues. This aims to suggest that organic residues are mainly formed in regions of molecular clouds exposed to UV light or cosmic rays. This study shows an organic residue formation involving glyoxal ice and H atoms. While the hydrogenation of glyoxal at 10 K leads mainly to small molecules such as CO and H2CO and CH3OH, we show that the heating of the hydrogenated ice in the 10–300 K temperature range leads to solid residues whose structure is similar to that of glycolaldehyde but they remain stable in solid phase at 300 K and atmospheric pressure. The analysis of the IR data shows that the organic residues formed through the thermal processing of CHOCHO + H reaction would be a mixture of hydroxypyruvaldehyde and methyl glyoxylate, two solid organics whose formation starts with an H-abstraction from glyoxal to form CHOCO• radical which recombines to •CH2OH and •OCH3 radicals. These latter may be formed and trapped in glyoxal ice as secondary products from H2CO + H secondary reaction.
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Kerridge, J. F. "Interstellar Molecules in Meteorites". Symposium - International Astronomical Union 135 (1989): 383–88. http://dx.doi.org/10.1017/s0074180900125392.
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Substantial enrichment of deuterium, D, in certain components of chondritic meteorites is interpreted as a record of isotopic fractionation during ion-molecule reactions at the very low temperatures characteristic of dense interstellar clouds. Whether those meteorites still contain the actual molecules that were synthesised in the presolar interstellar medium, or whether the interstellar material was recycled into a later generation of molecules within the early solar system is not known.
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Chuang, K. J. "Solid-state production of complex organic molecules: H-atom addition versus UV irradiation". Proceedings of the International Astronomical Union 13, S332 (marzec 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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Baiano, Carmen, Jacopo Lupi, Nicola Tasinato, Cristina Puzzarini i Vincenzo Barone. "The Role of State-of-the-Art Quantum-Chemical Calculations in Astrochemistry: Formation Route and Spectroscopy of Ethanimine as a Paradigmatic Case". Molecules 25, nr 12 (22.06.2020): 2873. http://dx.doi.org/10.3390/molecules25122873.
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The gas-phase formation and spectroscopic characteristics of ethanimine have been re-investigated as a paradigmatic case illustrating the accuracy of state-of-the-art quantum-chemical (QC) methodologies in the field of astrochemistry. According to our computations, the reaction between the amidogen, NH, and ethyl, C2H5, radicals is very fast, close to the gas-kinetics limit. Although the main reaction channel under conditions typical of the interstellar medium leads to methanimine and the methyl radical, the predicted amount of the two E,Z stereoisomers of ethanimine is around 10%. State-of-the-art QC and kinetic models lead to a [E−CH3CHNH]/[Z−CH3CHNH] ratio of ca. 1.4, slightly higher than the previous computations, but still far from the value determined from astronomical observations (ca. 3). An accurate computational characterization of the molecular structure, energetics, and spectroscopic properties of the E and Z isomers of ethanimine combined with millimeter-wave measurements up to 300 GHz, allows for predicting the rotational spectrum of both isomers up to 500 GHz, thus opening the way toward new astronomical observations.
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Tennis, Jessica, Jean-Christophe Loison i Eric Herbst. "Radiative Association between Neutral Radicals in the Interstellar Medium: CH3 + CH3O". Astrophysical Journal 922, nr 2 (26.11.2021): 133. http://dx.doi.org/10.3847/1538-4357/ac3239.
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Abstract Uncertainties in the production mechanisms of interstellar complex organic molecules call for a precise investigation of gas-phase synthetic routes for these molecules, especially at low temperatures. Here, we report a study of the gas-phase formation of dimethyl ether from the neutral radicals methyl and methoxy via the process of radiative association. This process may be important to synthesize dimethyl ether and species such as methyl formate, for which dimethyl ether is a precursor. The reaction is found to be rapid by the standards of radiative association, especially at 10 K, where its rate coefficient is calculated by two different methods to be 3 × 10−11 or 2 × 10−10 cm3 s−1; the lower rate is calculated with a more precise theory and is likely more accurate. Insertion of this reaction into the Nautilus network is found not to explain fully the abundance of dimethyl ether in cold and prestellar cores, especially in those cores with the highest dimethyl ether abundances.
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Wu, Mengqi, Jiangbin Huang, Xiaoqing Wu, Qifeng Hou, Dongfeng Zhao i Feng Zhang. "Reaction Kinetics of CN + Toluene and Its Implication on the Production of Aromatic Nitriles in the Taurus Molecular Cloud and Titan’s Atmosphere". Astrophysical Journal 950, nr 1 (1.06.2023): 55. http://dx.doi.org/10.3847/1538-4357/acca81.
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Abstract Reactions between cyano radicals and aromatic hydrocarbons are believed to be important pathways for the formation of aromatic nitriles in the interstellar medium (ISM) including those identified in the Taurus molecular cloud (TMC-1). Aromatic nitriles might participate in the formation of polycyclic aromatic nitrogen-containing hydrocarbons (PANHs) in Titan's atmosphere. Here, ab initio kinetic simulations reveal a high efficiency of ∼10−10 cm3 s−1 and the competition of the different products of the CN + toluene reaction at 30–1800 K and 10−7–100 atm. In the star-forming region of the TMC-1 environment, the product yields of benzonitrile and tolunitriles for CN reacting with toluene are approximately 17% and 83%, respectively. Detections of the main products, tolunitriles, can serve as proxies for the undetected toluene in the ISM due to their much larger dipole moments. Competition between bimolecular and unimolecular products is extremely intense in the warmer and denser PANH-forming region of Titan's stratosphere. Computational results show that the fractions of tolunitriles, adducts, and benzonitrile are 19%–68%, 15%–64%, and 17%, respectively, at 150–200 K and 0.0001–0.001 atm (Titan's stratosphere). Then, benzonitrile and tolunitriles may contribute to the formation of PANHs by consecutive C2H additions. The kinetic information of aromatic nitriles for the CN + toluene reaction calculated here helps to explain the formation mechanism of polycyclic aromatic hydrocarbons or PANHs under different interstellar environments and constrains corresponding astrochemical models.
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Vastel, C., J. C. Loison, V. Wakelam i B. Lefloch. "Isocyanogen formation in the cold interstellar medium". Astronomy & Astrophysics 625 (maj 2019): A91. http://dx.doi.org/10.1051/0004-6361/201935010.
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Context. Cyanogen (NCCN) is the simplest member of the dicyanopolyynes group, and has been proposed as a major source of the CN radical observed in cometary atmospheres. Although not detected through its rotational spectrum in the cold interstellar medium, this very stable species is supposed to be very abundant. Aims. The chemistry of cyanogen in the cold interstellar medium can be investigated through its metastable isomer, CNCN (isocyanogen). Its formation may provide a clue on the widely abundant CN radical observed in cometary atmospheres. Methods. We performed an unbiased spectral survey of the L1544 proto-typical prestellar core, using the IRAM-30 m and have analysed, for this paper, the nitrogen chemistry that leads to the formation of isocyanogen. We report on the first detection of CNCN, NCCNH+, C3N, CH3CN, C2H3CN, and H2CN in L1544. We built a detailed chemical network for NCCN/CNCN/HC2N2+ involving all the nitrogen bearing species detected (CN, HCN, HNC, C3N, CNCN, CH3CN, CH2CN, HCCNC, HC3N, HNC3, H2CN, C2H3CN, HCNH+, HC3NH+) and the upper limits on C4N, C2N. The main cyanogen production pathways considered in the network are the CN + HNC and N + C3N reactions. Results. The comparison between the observations of the nitrogen bearing species and the predictions from the chemical modelling shows a very good agreement, taking into account the new chemical network. The expected cyanogen abundance is greater than the isocyanogen abundance by a factor of 100. Although cyanogen cannot be detected through its rotational spectrum, the chemical modelling predicts that it should be abundant in the gas phase and hence might be traced through the detection of isocyanogen. It is however expected to have a very low abundance on the grain surfaces compared to HCN.
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El Hadki, Hamza, Zouhair Lakbaibi, Mohammed Salah, Khadija Marakchi, Oum Keltoum Kabbaj, Maria Luisa Senent i Najia Komiha. "The formation of interstellar organic molecules: H2C3O A DFT and ELF theoretical study". Mediterranean Journal of Chemistry 9, nr 3 (28.09.2019): 175–89. http://dx.doi.org/10.13171/mjc93190924420nk.
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This quantum study at B3LYP/6-311 ++ G (d, p) with ELF analysis were performed in order to understand the formation of propynal and cyclopropenone, two molecules detected in the interstellar medium. The formation of these molecules is supposed to be through reactions between carbon monoxide (CO) and acetylene (C2H2) in the cold conditions of interstellar clouds. All the structures, reagents, products and transition states, have been optimized and the geometrical parameters are given as well as the dipole moments. The reaction paths are elaborated and discussed here using the IRC method implemented in the Gaussian program. The determined activation energies allow an estimation of the rate constants. The ELF analysis performed here seems to be a valuable tool for screening the evolution of the bonds during the formation processes. The two reactions probably occur in one step. The propadienone, another possible isomer, has been also studied. It is formed through a third reaction. A stable triplet ground state of this molecule, the thermodynamic consideration and a small dipole moment can explain the fact that it is not detected yet in the interstellar medium. M06-2X and WB97XD functional were also used for comparing results.
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Largo, Antonio, Pilar Redondo i Carmen Barrientos. "Theoretical study of possible ion-molecule reactions leading to precursors of glycine in the interstellar medium". International Journal of Quantum Chemistry 98, nr 4 (2004): 355–60. http://dx.doi.org/10.1002/qua.20070.
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Awad, Zainab, Audrey Coutens, Serena Viti i Jonathan Holdship. "On the formation of deuterated methyl formate in hot corinos". Monthly Notices of the Royal Astronomical Society 506, nr 1 (22.06.2021): 1019–30. http://dx.doi.org/10.1093/mnras/stab1759.
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ABSTRACT Methyl formate, HCOOCH3, and many of its isotopologues have been detected in astrophysical regions with considerable abundances. However, the recipe for the formation of this molecule and its isotopologues is not yet known. In this work, we attempt to investigate, theoretically, the successful recipe for the formation of interstellar HCOOCH3 and its deuterated isotopologues. We used the gas–grain chemical model, uclchem, to examine the possible routes of formation of methyl formate on grain surfaces and in the gas-phase in low-mass star-forming regions. Our models show that radical–radical association on grains are necessary to explain the observed abundance of DCOOCH3 in the protostar IRAS 16293–2422. H-D substitution reactions on grains significantly enhance the abundances of HCOOCHD2, DCOOCHD2, and HCOOCD3. The observed abundance of HCOOCHD2 in IRAS 16293–2422 can only be reproduced if H-D substitution reactions are taken into account. However, HCOOCH2D remain underestimated in all of our models. The deuteration of methyl formate appears to be more complex than initially thought. Additional studies, both experimentally and theoretically, are needed for a better understanding of the interstellar formation of these species.
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Rivilla, V. M., I. Jiménez-Serra, J. García de la Concepción, J. Martín-Pintado, L. Colzi, L. F. Rodríguez-Almeida, B. Tercero i in. "Detection of the cyanomidyl radical (HNCN): a new interstellar species with the NCN backbone". Monthly Notices of the Royal Astronomical Society: Letters 506, nr 1 (2.07.2021): L79—L84. http://dx.doi.org/10.1093/mnrasl/slab074.
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ABSTRACT We report here the first detection in the interstellar medium of the cyanomidyl radical (HNCN). Using the Yebes 40m and the IRAM 30m telescopes, we have targeted the doublets of the N = 2–1, 4–3, 5–4, 6–5, and 7–6 transitions of HNCN towards the molecular cloud G+0.693-0.027. We have detected three unblended lines of HNCN, these are the N = 6–5 doublet and one line of the N = 4–3 transition. Additionally, we present one line of the N = 5–4 transition partially blended with emission from other species. The local thermodynamic equilibrium best fit to the data gives a molecular abundance of (0.91 ± 0.05) × 10−10 with respect to H2. The relatively low abundance of this species in G+0.693-0.027 and its high reactivity suggest that HNCN is possibly produced by gas-phase chemistry. Our work shows that this highly reactive molecule is present in interstellar space, and thus it represents a plausible precursor of larger prebiotic molecules with the nitrogen–carbon–nitrogen backbone such as cyanamide (NH2CN), carbodiimide (HNCNH), and formamidine (NH2CHNH).
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Mcgonagle, Douglas, William Irvine i Young Minh. "Nitrogen Sulfide (NS) in Star Forming Regions". Symposium - International Astronomical Union 150 (1992): 227–30. http://dx.doi.org/10.1017/s0074180900090070.
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Gas phase models of ion molecule chemistry have been rather successful in matching the observed abundances of small interstellar molecules containing carbon, hydrogen, and oxygen. However, the situation is somewhat less clear for nitrogen-containing species, partly because the important initiating reaction N+ + H2 is slightly endothermic; and for sulfur-containing molecules, where it remains uncertain whether it is necessary to invoke surface reactions on grains to match the observed abundances. As a relatively simple species, the abundance of nitrogen sulfide should provide a good test of the models of the coupled chemistry of nitrogen and sulfur. Until very recently only two molecules containing both these elements were known in the interstellar medium, NS and HNCS, and both have been observed only in Sgr B2. We have therefore undertaken a survey for interstellar NS in Galactic molecular clouds using the FCRAO 14-meter telescope. The 2Π1/2, J = 5/2 → 3/2, transition has in fact been detected in many regions of massive star formation (see table).
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Dagdigian, Paul J. "Collisional excitation of the formyl radical (HCO) by molecular hydrogen". Monthly Notices of the Royal Astronomical Society 498, nr 4 (14.09.2020): 5361–66. http://dx.doi.org/10.1093/mnras/staa2803.
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ABSTRACT This paper addresses the need for accurate rate coefficients for transitions between fine- and hyperfine-structure resolved rotational transitions in the formyl (HCO) radical induced by collisions with the two nuclear spin modifications of H2, the dominant molecule in the interstellar medium (ISM). These rate coefficients, as well as radiative transition rate coefficients, are required for accurate determination of the abundance of HCO in the ISM. Time-independent close-coupling quantum scattering calculations have been used to compute rate coefficients for (de-)excitation of HCO in collisions with para- and ortho-H2. These calculations utilized a potential energy surface for the interaction of HCO with H2 recently computed by the explicitly correlated RCCSD(T)-F12a coupled-cluster method. Rate coefficients for temperatures ranging from 5 to 400 K were calculated for all transitions among the fine and hyperfine levels associated with the first 22 rotational levels of HCO, whose energies are less than or equal to 144 K.
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Indriolo, Nick. "Absorption-line Observations of H3+ and CO in Sight Lines Toward the Vela and W28 Supernova Remnants". Astrophysical Journal 950, nr 1 (1.06.2023): 64. http://dx.doi.org/10.3847/1538-4357/acc6c4.
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Abstract Supernova remnants act as particle accelerators, providing the cosmic-ray protons that permeate the interstellar medium and initiate the ion–molecule reactions that drive interstellar chemistry. Enhanced fluxes of cosmic-ray protons in close proximity to supernova remnants have been inferred from observations tracing particle interactions with nearby molecular gas. Here I present observations of H 3 + and CO absorption, molecules that serve as tracers of the cosmic-ray ionization rate and gas density, respectively, in sight lines toward the W28 and Vela supernova remnants. Cosmic-ray ionization rates inferred from these observations range from about 2 to 10 times the average value in Galactic diffuse clouds (∼3 × 10−16 s−1), suggesting that the gas being probed is experiencing an elevated particle flux. While it is difficult to constrain the line-of-sight locations of the absorbing gas with respect to the supernova remnants, these results are consistent with a scenario where cosmic rays are diffusing away from the acceleration site and producing enhanced ionization rates in the surrounding medium.
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García de la Concepción, Juan, Cristina Puzzarini, Vincenzo Barone, Izaskun Jiménez-Serra i Octavio Roncero. "Formation of Phosphorus Monoxide (PO) in the Interstellar Medium: Insights from Quantum-chemical and Kinetic Calculations". Astrophysical Journal 922, nr 2 (29.11.2021): 169. http://dx.doi.org/10.3847/1538-4357/ac1e94.
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Abstract In recent years, phosphorus monoxide (PO), an important molecule for prebiotic chemistry, has been detected in star-forming regions and in the comet 67P/Churyumov-Gerasimenko. These studies have revealed that, in the interstellar medium (ISM), PO is systematically the most abundant P-bearing species, with abundances that are about one to three times greater than those derived for phosphorus nitride (PN), the second-most abundant P-containing molecule. The reason why PO is more abundant than PN remains still unclear. Experimental studies with phosphorus in the gas phase are not available, probably because of the difficulties in dealing with its compounds. Therefore, the reactivity of atomic phosphorus needs to be investigated using reliable computational tools. To this end, state-of-the-art quantum-chemical computations have been employed to evaluate accurate reaction rates and branching ratios for the P + OH → PO + H and P + H2O → PO + H2 reactions in the framework of a master equation approach based on ab initio transition state theory. The hypothesis that OH and H2O can be potential oxidizing agents of atomic phosphorus is based on the ubiquitous presence of H2O in the ISM. Its destruction then produces OH, which is another very abundant species. While the reaction of atomic phosphorus in its ground state with water is not a relevant source of PO because of emerged energy barriers, the P + OH reaction represents an important formation route of PO in the ISM. Our kinetic results show that this reaction follows an Arrhenius–Kooij behavior, and thus its rate coefficients (α = 2.28 × 10−10 cm3 molecule−1 s−1, β = 0.16 and γ = 0.37 K) increase by increasing the temperature.
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Qasim, D., T. Lamberts, J. He, K. J. Chuang, G. Fedoseev, S. Ioppolo, A. C. A. Boogert i H. Linnartz. "Extension of the HCOOH and CO2 solid-state reaction network during the CO freeze-out stage: inclusion of H2CO". Astronomy & Astrophysics 626 (czerwiec 2019): A118. http://dx.doi.org/10.1051/0004-6361/201935068.
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Context. Formic acid (HCOOH) and carbon dioxide (CO2) are simple species that have been detected in the interstellar medium. The solid-state formation pathways of these species under experimental conditions relevant to prestellar cores are primarily based off of weak infrared transitions of the HOCO complex and usually pertain to the H2O-rich ice phase, and therefore more experimental data are desired. Aims. Here, we present a new and additional solid-state reaction pathway that can form HCOOH and CO2 ice at 10 K “non-energetically” in the laboratory under conditions related to the “heavy” CO freeze-out stage in dense interstellar clouds, i.e., by the hydrogenation of an H2CO:O2 ice mixture. This pathway is used to piece together the HCOOH and CO2 formation routes when H2CO or CO reacts with H and OH radicals. Methods. Temperature programmed desorption – quadrupole mass spectrometry (TPD-QMS) is used to confirm the formation and pathways of newly synthesized ice species as well as to provide information on relative molecular abundances. Reflection absorption infrared spectroscopy (RAIRS) is additionally employed to characterize reaction products and determine relative molecular abundances. Results. We find that for the conditions investigated in conjunction with theoretical results from the literature, H + HOCO and HCO + OH lead to the formation of HCOOH ice in our experiments. Which reaction is more dominant can be determined if the H + HOCO branching ratio is more constrained by computational simulations, as the HCOOH:CO2 abundance ratio is experimentally measured to be around 1.8:1. H + HOCO is more likely than OH + CO (without HOCO formation) to form CO2. Isotope experiments presented here further validate that H + HOCO is the dominant route for HCOOH ice formation in a CO-rich CO:O2 ice mixture that is hydrogenated. These data will help in the search and positive identification of HCOOH ice in prestellar cores.
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Santos, Julia C., Ko-Ju Chuang, Thanja Lamberts, Gleb Fedoseev, Sergio Ioppolo i Harold Linnartz. "First Experimental Confirmation of the CH3O + H2CO → CH3OH + HCO Reaction: Expanding the CH3OH Formation Mechanism in Interstellar Ices". Astrophysical Journal Letters 931, nr 2 (1.06.2022): L33. http://dx.doi.org/10.3847/2041-8213/ac7158.
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Abstract The successive addition of H atoms to CO in the solid phase has been hitherto regarded as the primary route to form methanol in dark molecular clouds. However, recent Monte Carlo simulations of interstellar ices alternatively suggested the radical-molecule H-atom abstraction reaction CH3O + H2CO → CH3OH + HCO, in addition to CH3O + H → CH3OH, as a very promising and possibly dominating (70%–90%) final step to form CH3OH in those environments. Here, we compare the contributions of these two steps leading to methanol by experimentally investigating hydrogenation reactions on H2CO and D2CO ices, which ensures comparable starting points between the two scenarios. The experiments are performed under ultrahigh vacuum conditions and astronomically relevant temperatures, with H:H2CO (or D2CO) flux ratios of 10:1 and 30:1. The radical-molecule route in the partially deuterated scenario, CHD2O + D2CO → CHD2OD + DCO, is significantly hampered by the isotope effect in the D-abstraction process, and can thus be used as an artifice to probe the efficiency of this step. We observe a significantly smaller yield of D2CO + H products in comparison to H2CO + H, implying that the CH3O-induced abstraction route must play an important role in the formation of methanol in interstellar ices. Reflection-absorption infrared spectroscopy and temperature-programmed desorption-quadrupole mass spectrometry analyses are used to quantify the species in the ice. Both analytical techniques indicate constant contributions of ∼80% for the abstraction route in the 10–16 K interval, which agrees well with the Monte Carlo calculations. Additional H2CO + D experiments confirm these conclusions.
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Balucani, Nadia. "Gas-phase prebiotic chemistry in extraterrestrial environments". Proceedings of the International Astronomical Union 5, H15 (listopad 2009): 682–83. http://dx.doi.org/10.1017/s1743921310010938.
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AbstractA variety of molecular species up to complex polyatomic molecules/radicals have been identified in many extraterrestrial gaseous environments, including interstellar clouds, cometary comae and planetary atmospheres. Amongst the identified molecules/radicals, a large percentage are organic in nature and encompass also prebiotic molecules. Different types of microscopic processes are believed to be involved in their formation, including surface processes, ion- and radical- molecule reactions. A thorough characterization of such a complex chemistry relies on a multi-disciplinary approach, where the observations are complemented by accurate chemical modeling. Unfortunately, a literature survey reveals that only a small percentage of the elementary reactions considered in the available models have been characterized in laboratory experiments. In this contribution, a brief overview will be given of recent experimental techniques that have allowed us to reach a better description of neutral-neutral gas-phase reactions, which might be responsible for the formation of simple prebiotic molecules.
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Garrod, Robin T. "Simulations of branched carbon-chain chemistry in star-forming regions". Proceedings of the International Astronomical Union 13, S332 (marzec 2017): 403–8. http://dx.doi.org/10.1017/s174392131700775x.
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AbstractThe detection of iso-propyl cyanide (i-C3H7CN) toward the Galactic Center hot-core source Sgr B2(N) (by Belloche et al. 2014) marked the first interstellar detection of an aliphatic molecule with a branched carbon-chain structure. Surprisingly, this branched form was found to have an almost equal abundance with its straight-chain homologue, normal-propyl cyanide (i:n = 0.40 ± 0.06). The detection of this first example of an interstellar molecule with a side-chain raises the question as to how prominent such structures may be in interstellar chemistry, and whether the large branched-to-straight chain ratio is maintained for even larger molecules.Here are presented recently published models that simulate the chemistry occurring in Sgr B2(N) using a chemical network that explicitly includes the straight-chain and branched forms of propyl cyanide (normal/iso) and butyl cyanide (normal/iso/sec/tert), as well as butane (n/i) and pentane (n/i/neo). Formation is assumed to occur on dust-grain surfaces, but a full complement of destruction mechanisms is included both on the grains and in the gas phase.The models suggest that branched structures become increasingly dominant as molecular sizes increase. In the case of butyl cyanide, the sec form is at least ∼2 times more abundant than the straight-chain normal form, and together the branched forms dominate normal-butyl cyanide by a factor of at least 3. The results for the larger alkanes suggest similarly large ratios of branched to straight-chain molecules. A key set of reactions in the surface/ice chemistry of interstellar nitriles is found to be the addition of the CN radical to unsaturated hydrocarbons, especially acetylene and ethene. The models also predict that the dominant, sec form of butyl cyanide reaches a peak abundance equal to that of n-propyl cyanide, albeit with a smaller emission radius. This makes s-C4H9CN a good candidate for detection. New ALMA observations to search for this molecule are ongoing.
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Coutens, A., N. F. W. Ligterink, J. C. Loison, V. Wakelam, H. Calcutt, M. N. Drozdovskaya, J. K. Jørgensen, H. S. P. Müller, E. F. van Dishoeck i S. F. Wampfler. "The ALMA-PILS survey: First detection of nitrous acid (HONO) in the interstellar medium". Astronomy & Astrophysics 623 (marzec 2019): L13. http://dx.doi.org/10.1051/0004-6361/201935040.
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Nitrogen oxides are thought to play a significant role as a nitrogen reservoir and to potentially participate in the formation of more complex species. Until now, only NO, N2O, and HNO have been detected in the interstellar medium. We report the first interstellar detection of nitrous acid (HONO). Twelve lines were identified towards component B of the low-mass protostellar binary IRAS 16293–2422 with the Atacama Large Millimeter/submillimeter Array, at the position where NO and N2O have previously been seen. A local thermodynamic equilibrium model was used to derive the column density (∼9 × 1014 cm−2 in a 0 .″5 beam) and excitation temperature (∼100 K) of this molecule. HNO, NO2, NO+, and HNO3 were also searched for in the data, but not detected. We simulated the HONO formation using an updated version of the chemical code Nautilus and compared the results with the observations. The chemical model is able to reproduce satisfactorily the HONO, N2O, and NO2 abundances, but not the NO, HNO, and NH2OH abundances. This could be due to some thermal desorption mechanisms being destructive and therefore limiting the amount of HNO and NH2OH present in the gas phase. Other options are UV photodestruction of these species in ices or missing reactions potentially relevant at protostellar temperatures.
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Fox, A., A. B. Raksit, S. Dheandhanoo i D. K. Bohme. "Selected-ion flow tube studies of reactions of the radical cation (HC3N)+• in the interstellar chemical synthesis of cyanoacetylene". Canadian Journal of Chemistry 64, nr 2 (1.02.1986): 399–403. http://dx.doi.org/10.1139/v86-064.
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The radical cation (HC3N)+• was produced in a Selected-Ion Flow Tube (SIFT) apparatus from cyanoacetylene by electron impact and reacted at room temperature in helium buffer gas with a selection of molecules including H2, CO, HCN, CH4, H2O, O2, HC3N, C2H2, OCS, C2H4, and C4H2. The observed reactions exhibited a wide range of reactivity and a variety of pathways including charge transfer, hydrogen atom transfer, proton transfer, and association. Association reactions were observed with CO, O2, HCN, and HC3N. With the latter two molecules association was observed to proceed close to the collision limit, which is suggestive of covalent bond formation perhaps involving azine-like N—N bonds. For HC3N an equally rapid association has been observed by Buckley etal. with ICR (Ion Cyclotron Resonance) measurements at low pressures and this is suggestive of radiative association. The hydrogen atom transfer reaction of ionized cyanoacetylene with H2 is slow while similar reactions with CH4 and H2O are fast. The reaction with CO fails to transfer a proton. These results have implications for synthetic schemes for cyanoacetylene as proposed in recent models of the chemistry of interstellar gas clouds. Proton transfer was also observed to be curiously unfavourable with all other molecules having a proton affinity higher than (C3N)•. Also, hydrogen-atom transfer was inefficient with the polar molecules HCN and HC3N. These results suggest that interactions at close separations may lead to preferential alignment of the reacting ion and molecule which is not suited for proton transfer or hydrogen atom transfer.
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Castellanos, P., A. Candian, H. Andrews i A. G. G. M. Tielens. "Photoinduced polycyclic aromatic hydrocarbon dehydrogenation". Astronomy & Astrophysics 616 (sierpień 2018): A167. http://dx.doi.org/10.1051/0004-6361/201833221.
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The physical and chemical conditions in photodissociation regions (PDRs) are largely determined by the influence of far ultraviolet radiation. Far-UV photons can efficiently dissociate molecular hydrogen, a process that must be balanced at the HI/H2 interface of the PDR. Given that reactions involving hydrogen atoms in the gas phase are highly inefficient under interstellar conditions, H2 formation models mostly rely on catalytic reactions on the surface of dust grains. Additionally, molecular hydrogen formation in polycyclic aromatic hydrocarbons (PAHs) through the Eley–Rideal mechanism has been considered as well, although it has been found to have low efficiency in PDR fronts. In a previous work, we have described the possibility of efficient H2 release from medium to large sized PAHs upon photodissociation, with the exact branching between H-/H2-loss reactions being molecule dependent. Here, we investigate the astrophysical relevance of this process, by using a model for the photofragmentation of PAHs under interstellar conditions. We focus on three PAHs cations (coronene, ovalene, and circumcoronene), which represent three possibilities in the branching of atomic and molecular hydrogen losses. We find that, for ovalene (H2-loss dominated) the rate coefficient for H2 formation reaches values of the same order as H2 formation in dust grains. This result suggests that this hitherto disregarded mechanism can account, at least partly, for the high level of molecular hydrogen formation in dense PDRs.
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Satta, Mauro, Mattea Carmen Castrovilli, Francesca Nicolanti, Anna Rita Casavola, Carlo Mancini Terracciano i Antonella Cartoni. "Perspectives of Gas Phase Ion Chemistry: Spectroscopy and Modeling". Condensed Matter 7, nr 3 (21.07.2022): 46. http://dx.doi.org/10.3390/condmat7030046.
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The study of ions in the gas phase has a long history and has involved both chemists and physicists. The interplay of their competences with the use of very sophisticated commercial and/or homemade instrumentations and theoretical models has improved the knowledge of thermodynamics and kinetics of many chemical reactions, even if still many stages of these processes need to be fully understood. The new technologies and the novel free-electron laser facilities based on plasma acceleration open new opportunities to investigate the chemical reactions in some unrevealed fundamental aspects. The synchrotron light source can be put beside the FELs, and by mass spectrometric techniques and spectroscopies coupled with versatile ion sources it is possible to really change the state of the art of the ion chemistry in different areas such as atmospheric and astro chemistry, plasma chemistry, biophysics, and interstellar medium (ISM). In this manuscript we review the works performed by a joint combination of the experimental studies of ion–molecule reactions with synchrotron radiation and theoretical models adapted and developed to the experimental evidence. The review concludes with the perspectives of ion–molecule reactions by using FEL instrumentations as well as pump probe measurements and the initial attempt in the development of more realistic theoretical models for the prospective improvement of our predictive capability.
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Motiyenko, R. A., A. Belloche, R. T. Garrod, L. Margulès, H. S. P. Müller, K. M. Menten i J. C. Guillemin. "Millimeter- and submillimeter-wave spectroscopy of thioformamide and interstellar search toward Sgr B2(N)". Astronomy & Astrophysics 642 (październik 2020): A29. http://dx.doi.org/10.1051/0004-6361/202038723.
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Context. Thioformamide NH2CHS is a sulfur-bearing analog of formamide NH2CHO. The latter was detected in the interstellar medium back in the 1970s. Most of the sulfur-containing molecules detected in the interstellar medium are analogs of corresponding oxygen-containing compounds. Therefore, thioformamide is an interesting candidate for a search in the interstellar medium. Aims. A previous study of the rotational spectrum of thioformamide was limited to frequencies below 70 GHz and to transitions with J ≤ 3. The aim of this study is to provide accurate spectroscopic parameters and rotational transition frequencies for thioformamide to enable astronomical searches for this molecule using radio telescope arrays at millimeter wavelengths. Methods. The rotational spectrum of thioformamide was measured and analyzed in the frequency range 150−660 GHz using the Lille spectrometer. We searched for thioformamide toward the high-mass star-forming region Sagittarius (Sgr) B2(N) using the ReMoCA spectral line survey carried out with the Atacama Large Millimeter/submillimeter Array. Results. Accurate rigid rotor and centrifugal distortion constants were obtained from the analysis of the ground state of parent, 34S, 13C, and 15N singly substituted isotopic species of thioformamide. In addition, for the parent isotopolog, the lowest two excited vibrational states, v12 = 1 and v9 = 1, were analyzed using a model that takes Coriolis coupling into account. Thioformamide was not detected toward the hot cores Sgr B2(N1S) and Sgr B2(N2). The sensitive upper limits indicate that thioformamide is nearly three orders of magnitude at least less abundant than formamide. This is markedly different from methanethiol, which is only about two orders of magnitude less abundant than methanol in both sources. Conclusions. The different behavior shown by methanethiol versus thioformamide may be caused by the preferential formation of the latter (on grains) at late times and low temperatures, when CS abundances are depressed. This reduces the thioformamide-to-formamide ratio, because the HCS radical is not as readily available under these conditions.
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BRÜCK, Thomas B., Maria Francesca GERINI, Enrico BACIOCCHI i Patricia J. HARVEY. "Oxidation of thioanisole and p-methoxythioanisole by lignin peroxidase: kinetic evidence of a direct reaction between compound II and a radical cation". Biochemical Journal 374, nr 3 (15.09.2003): 761–66. http://dx.doi.org/10.1042/bj20030487.
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The reaction of H2O2 with thioanisole and p-methoxythioanisole catalysed by lignin peroxidase from Phanerochaete chrysosporium has been studied spectrophotometrically under turnover and single turnover conditions with a stopped-flow apparatus. Pre-formed lignin peroxidase compounds I and II are each able to react with the sulphides to form a sulphide radical cation. The radical cation is then converted into the sulphoxide either by reaction with the medium or by reaction with compound II. This is the first report of a direct reaction between compound II and the substrate radical cation. With thioanisole, significant enantiomeric selectivity and high oxygen incorporation in the sulphoxide are obtained because compound II is preferentially reduced by the enzyme-bound thioanisole radical cation compared with the neutral substrate. By contrast, with p-methoxythioanisole, the data imply formation of an intermediate ternary complex comprising compound II, radical cation and neutral substrate, such that a chain of electron transfer reactions starting from neutral molecule and progressing to oxidized haem via substrate radical cation is facilitated, yielding the native enzyme and two molecules of p-methoxythioanisole radical cation as products. The reactions of compounds I and II with sulphides imply flexing of the apoprotein moiety during catalysis.