Gas-phase reactivity of CH3OH+OH down to 11.7 K: Astrophysical implications

2019 ◽  
Vol 15 (S350) ◽  
pp. 365-367
Author(s):  
Antonio J. Ocaña ◽  
Sergio Blázquez ◽  
Daniel González ◽  
Alexey Potapov ◽  
Bernabé Ballesteros ◽  
...  

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.

2021 ◽  
Author(s):  
Nadia Balucani

<p> </p> <p>How did life emerge from inanimate matter? The processes that led from complex organic molecules to the first self-replicating systems are no longer at play and we cannot easily reconstruct them because we do not have a geological record of the period when the transition from simple molecules to the very first forms of “life” have occurred. The presence of stable hydrosphere is considered as the first milestone in the timeline of the abiotic origin of life theory, with the second milestone being the massive accumulation of organic compounds necessary for the transition from organic chemistry to the biochemistry of life. But how Earth became so rich in complex organic molecules – up to the point that life spontaneously evolved from them - is still a matter of debate. At that stage, the abundance of liquid water, indeed, represents an obstacle for organic synthesis. Two theories have been suggested to solve this paradox, which are usually referred to as <em>endogenous synthesis</em> and <em>exogenous synthesis</em> scenarios [1]. But in both cases, prebiotic molecules (that is, molecules which are simple to be formed in abiotic processes but contain the functional groups typical of biological molecules or have the capability to easily evolve into them) are formed in gaseous media. Indeed, gas-phase prebiotic molecules have been observed in the upper atmosphere of Titan, the massive moon of Saturn, as well as in the interstellar clouds and cometary comae.</p> <p>The comprehension of the chemical processes that lead from simple atomic/diatomic species to prebiotic complex chemicals is an important part of the study on the origin of life. The study of these preliminary steps might seem relatively simple compared to the characterization of the other unknown phenomena that have led to the first living organisms. Nevertheless, the formation mechanisms of many of the prebiotic molecules that we observe nowadays in proto-stellar clouds or comets/meteorites or planetary atmospheres are far from being understood, while a comprehension of those processes can certainly help to set the stage for the emergence of life to occur.</p> <p>For this reason, in our laboratory we have started a systematic investigation of gas-phase reactions leading to simple prebiotic molecules within the Italian National Project of Astrobiology—Life in Space—Origin, Presence, Persistence of Life in Space, from Molecules to Extremophiles [2].</p> <p>In particular, by combining an experimental and theoretical approach, we have investigated a series of bimolecular reactions under single collision conditions. The aim is to provide detailed information on the elementary reactions which are employed in photochemical models of planetary atmosphere and cometary comae [3]. In particular, we have investigated several reactive systems leading to the formation of nitriles (such as dicyanoacetylene) and imines (such as ethanimine), as well as reactive radicals that can further react in subsequent reactions. We have also investigated reactions involving nitrogen atoms and aromatic compounds (benzene, pyridine, toluene) to address the role of these compounds in the growth of N-containing aromatic compounds, a proxy of DNA and RNA bases. In this contribution, the main results concerning the reactions involving atomic nitrogen, N, or cyano radicals, CN, and cyanoacetylene, acrylonitrile, benzene, toluene and pyridine will be illustrated and the implications for prebiotic chemistry noted.</p> <p>[1] C. Chyba and C. Sagan. Nature 1992, 355, 125.</p> <p>[2] S. Onofri, N. Balucani, V. Barone et al. Astrobiology 2020, 20, 580. DOI: 10.1089/ast.2020.2247</p> <p>[3] N. Balucani. Physics of Life Reviews 2020, 34–35, 136. DOI: 10.1016/j.plrev.2019.03.0061571-0645</p>


2014 ◽  
Vol 168 ◽  
pp. 369-388 ◽  
Author(s):  
J. M. C. Rawlings ◽  
D. A. Williams ◽  
S. Viti ◽  
C. Cecchi-Pestellini ◽  
W. W. Duley

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.


2008 ◽  
Vol 4 (S251) ◽  
pp. 137-138 ◽  
Author(s):  
Alexandre Faure ◽  
Eric Josselin ◽  
Laurent Wiesenfeld ◽  
Cecilia Ceccarelli

AbstractA major difficulty in modelling the infrared and (sub)millimeter spectra of gas-phase complex organic molecules is the lack of state-to-state collisional rate coefficients. Accurate quantum or classical scattering calculations for large polyatomic species are indeed computationally highly challenging, particularly when both rotation and low frequency vibrations such as bending and torsional modes are involved. We briefly present here an approximate approach to estimate and/or extrapolate rotational and rovibrational rates for polyatomic molecules with many degrees of freedom.


Author(s):  
S Iglesias-Groth

Abstract We present the detection of fullerenes C60 and C70 in the star-forming region IC 348 of the Perseus molecular cloud. Mid-IR vibrational transitions of C60 and C70 in emission are found in Spitzer IRS spectra of individual stars (LRLL 1, 2, 58), in the averaged spectrum of three other cluster stars (LRLL 21, 31 and 67) and in spectra obtained at four interstellar locations distributed across the IC 348 region. Fullerene bands appear widely distributed in this region with higher strength in the lines-of-sight of stars at the core of the cluster. Emission features consistent with three most intense bands of the C$_{60}^+$ and with one of C$_{60}^-$ are also found in several spectra, and if ascribed to these ionized species it would imply ionization fractions at 20 and 10 %, respectively. The stars under consideration host protoplanetary disks, however the spatial resolution of the spectra is not sufficient to disentangle the presence of fullerenes in them. If fullerene abundances in the cloud were representative of IC 348 protoplanetary disks, C60, the most abundant of the two species, could host ∼ 0.1 % of the total available carbon in the disks. This should encourage dedicated searches in young disks with upcoming facilities as JWST. Fullerenes provide a reservoir of pentagonal and hexagonal carbon rings which could be important as building blocks of prebiotic molecules. Accretion of these robust molecules in early phases of planet formation may contribute to the formation of complex organic molecules in young planets.


2015 ◽  
Vol 112 (4) ◽  
pp. 965-970 ◽  
Author(s):  
Pierre de Marcellus ◽  
Cornelia Meinert ◽  
Iuliia Myrgorodska ◽  
Laurent Nahon ◽  
Thomas Buhse ◽  
...  

Evolved interstellar ices observed in dense protostellar molecular clouds may arguably be considered as part of precometary materials that will later fall on primitive telluric planets, bringing a wealth of complex organic compounds. In our laboratory, experiments reproducing the photo/thermochemical evolution of these ices are routinely performed. Following previous amino acid identifications in the resulting room temperature organic residues, we have searched for a different family of molecules of potential prebiotic interest. Using multidimensional gas chromatography coupled to time-of-flight mass spectrometry, we have detected 10 aldehydes, including the sugar-related glycolaldehyde and glyceraldehyde—two species considered as key prebiotic intermediates in the first steps toward the synthesis of ribonucleotides in a planetary environment. The presence of ammonia in water and methanol ice mixtures appears essential for the recovery of these aldehydes in the refractory organic residue at room temperature, although these products are free of nitrogen. We finally point out the importance of detecting aldehydes and sugars in extraterrestrial environments, in the gas phase of hot molecular clouds, and, more importantly, in comets and in primitive meteorites that have most probably seeded the Earth with organic material as early as 4.2 billion years ago.


2016 ◽  
Vol 119 (1) ◽  
pp. 5-18
Author(s):  
Ádám Illés ◽  
Mária Farkas ◽  
Gábor László Zügner ◽  
Gyula Novodárszki ◽  
Magdolna Mihályi ◽  
...  

2021 ◽  
Author(s):  
María Asensio ◽  
María Antiñolo ◽  
Sergio Blázquez ◽  
José Albaladejo ◽  
Elena Jiménez

Abstract. Saturated aldehydes, e.g. 2-methylbutanal (2MB, CH3CH2CH(CH3)C(O)H), are emitted into the atmosphere by several biogenic sources. The first step in the daytime atmospheric degradation of 2MB involves gas-phase reactions initiated by hydroxyl (OH) radicals, chlorine (Cl) atoms and/or sunlight. In this work, we report the rate coefficients for the gas-phase reaction of 2MB with OH (kOH) and Cl (kCl) together with the photolysis rate coefficient (J) in the ultraviolet solar actinic region in Valencia (Spain) at different times of the day. The temperature dependence of kOH was described in the 263–353 K range by the following Arrhenius expression: kOH(T)=(8.88±0.41)×10-12 exp[(331±14)/T] cm3 molecule-1 s-1. At 298 K, the reported kOH and kCl are (2.68±0.07)×10-11 cm3 molecule-1 s-1 and (2.16±0.16)×10-11 cm3 molecule-1 s-1. Identification and quantification of the gaseous products of the Cl-reaction and those from the photodissociation of 2MB were carried out in a smog chamber by different techniques (Fourier transform infrared spectroscopy, proton transfer time-of-flight mass spectrometry, and gas chromatography coupled to mass spectrometry). The formation and size distribution of secondary organic aerosols formed in the Cl-reaction was monitored by a fast mobility particle sizer spectrometer. A discussion on the relative importance of the first step in the daytime atmospheric degradation of 2MB is presented together with the impact of the degradation products in marine atmospheres.


2011 ◽  
Vol 11 (1) ◽  
pp. 2377-2405 ◽  
Author(s):  
M. E. Davis ◽  
J. B. Burkholder

Abstract. Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-3-hexen-1-ol ((Z)-CH3CH2CH=CHCH2CH2OH). (k1), 1-penten-3-ol (CH3CH2CH(OH)CH=CH2) (k2), (E)-2-penten-1-ol ((E)-CH3CH2CH=CHCH2OH) (k3), and (E)-2-hexen-1-ol ((E)-CH3CH2CH2CH=CHCH2OH) (k4), unsaturated alcohols that are emitted into the atmosphere following vegetation wounding, are reported. Rate coefficients were measured under pseudo-first-order conditions in OH over the temperature range 243–404 K at pressures between 20 and 100 Torr (He) using pulsed laser photolysis (PLP) to produce OH radicals and laser induced fluorescence (LIF) to monitor the OH temporal profile. The obtained rate coefficients were independent of pressure with negative temperature dependences that are well described by the Arrhenius expressions k1(T) = (1.3 ± 0.1) × 10−11 exp[(580 ± 10)/T]; k1(297K) = (1.06 ± 0.12) × 10−10 k2(T) = (6.8 ± 0.7) × 10−12 exp[(690 ± 20)/T]; k2(297K) = (7.12 ± 0.73) × 10−11 k3(T) = (6.8 ± 0.8) × 10−12 exp[(680 ± 20)/T]; k3(297K) = (6.76 ± 0.70) × 10−11 k4(T) = (5.4 ± 0.6) × 10−12 exp[(690 ± 20)/T]; k4(297K) = (6.15 ± 0.75) × 10−11 (in units of cm3 molecule−1 s−1). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. The rate coefficients obtained in this study are compared with literature values where possible.


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