scholarly journals Chemical complexity in the Horsehead photodissociation region

2014 ◽  
Vol 168 ◽  
pp. 103-127 ◽  
Author(s):  
Viviana V. Guzmán ◽  
Jérôme Pety ◽  
Pierre Gratier ◽  
Javier R. Goicoechea ◽  
Maryvonne Gerin ◽  
...  
Keyword(s):  
Interstellar Medium ◽  
Gas Phase ◽  
Thermal Desorption ◽  
Organic Molecules ◽  
Dense Core ◽  
High Spectral Resolution ◽  
Complex Molecules ◽  
Chemical Complexity ◽  
Clean Environment ◽  
Complex Organic

The interstellar medium is known to be chemically complex. Organic molecules with up to 11 atoms have been detected in the interstellar medium, and are believed to be formed on the ices around dust grains. The ices can be released into the gas-phase either through thermal desorption, when a newly formed star heats the medium around it and completely evaporates the ices; or through non-thermal desorption mechanisms, such as photodesorption, when a single far-UV photon releases only a few molecules from the ices. The first mechanism dominates in hot cores, hot corinos and strongly UV-illuminated PDRs, while the second dominates in colder regions, such as low UV-field PDRs. This is the case of the Horsehead were dust temperatures are ≃20–30 K, and therefore offers a clean environment to investigate the role of photodesorption. We have carried out an unbiased spectral line survey at 3, 2 and 1mm with the IRAM-30m telescope in the Horsehead nebula, with an unprecedented combination of bandwidth, high spectral resolution and sensitivity. Two positions were observed: the warm PDR and a cold condensation shielded from the UV field (dense core), located just behind the PDR edge. We summarize our recently published results from this survey and present the first detection of the complex organic molecules HCOOH, CH2CO, CH3CHO and CH3CCH in a PDR. These species together with CH3CN present enhanced abundances in the PDR compared to the dense core. This suggests that photodesorption is an efficient mechanism to release complex molecules into the gas-phase in far-UV illuminated regions.

scholarly journals Laboratory constraints on ice formation, restructuring and desorption

2015 ◽  
Vol 11 (A29A) ◽  
pp. 309-312
Author(s):  
Karin I. Öberg
Keyword(s):  
Gas Phase ◽  
Chemical Reactions ◽  
Organic Molecules ◽  
Protoplanetary Disks ◽  
Ice Formation ◽  
Circumstellar Dust ◽  
Dust Grains ◽  
Complex Molecules ◽  
Detailed Understanding ◽  
Complex Organic

AbstractIces form on the surfaces of interstellar and circumstellar dust grains though freeze-out of molecules and atoms from the gas-phase followed by chemical reactions. The composition, chemistry, structure and desorption properties of these ices regulate two important aspects of planet formation: the locations of major condensation fronts in protoplanetary disks (i.e. snow lines) and the formation efficiencies of complex organic molecules in astrophysical environments. The latter regulates the availability of prebiotic material on nascent planets. With ALMA it is possible to directly observe both (CO) snowlines and complex organics in protoplanetary disks. The interpretation of these observations requires a detailed understanding of the fundamental ice processes that regulate the build-up, evolution and desorption of icy grain mantles. This proceeding reviews how experiments on thermal CO and N2 ice desorption, UV photodesorption of CO ice, and CO diffusion in H2O ice have been used to guide and interpret astrochemical observations of snowlines and complex molecules.

scholarly journals Complex organic molecules along the accretion flow in isolated and externally irradiated protoplanetary disks

2014 ◽  
Vol 168 ◽  
pp. 389-421 ◽  
Author(s):  
Catherine Walsh ◽  
Eric Herbst ◽  
Hideko Nomura ◽  
T. J. Millar ◽  
Susanna Widicus Weaver
Keyword(s):  
Surface Chemistry ◽  
Gas Phase ◽  
Organic Molecules ◽  
Molecular Layer ◽  
Accretion Flow ◽  
Chemical Complexity ◽  
Outer Disk ◽  
Molecular Abundances ◽  
Grain Surface ◽  
Complex Organic

The birth environment of the Sun will have influenced the physical and chemical structure of the pre-solar nebula, including the attainable chemical complexity reached in the disk, important for prebiotic chemistry. The formation and distribution of complex organic molecules (COMs) in a disk around a T Tauri star is investigated for two scenarios: (i) an isolated disk, and (ii) a disk irradiated externally by a nearby massive star. The chemistry is calculated along the accretion flow from the outer disk inwards using a comprehensive network which includes gas-phase reactions, gas-grain interactions, and thermal grain-surface chemistry. Two simulations are performed, one beginning with complex ices and one with simple ices only. For the isolated disk, COMs are transported without major chemical alteration into the inner disk where they thermally desorb into the gas reaching an abundance representative of the initial assumed ice abundance. For simple ices, COMs can efficiently form on grain surfaces under the conditions in the outer disk. Gas-phase COMs are released into the molecular layer via photodesorption. For the irradiated disk, complex ices are also transported inwards; however, they undergo thermal processing caused by the warmer conditions in the irradiated disk which tends to reduce their abundance along the accretion flow. For simple ices, grain-surface chemistry cannot efficiently synthesise COMs in the outer disk because the necessary grain-surface radicals, which tend to be particularly volatile, are not sufficiently abundant on the grain surfaces. Gas-phase COMs are formed in the inner region of the irradiated disk via gas-phase chemistry induced by the desorption of strongly bound molecules such as methanol; hence, the abundances are not representative of the initial molecular abundances injected into the outer disk. These results suggest that the composition of comets formed in isolated disks may differ from those formed in externally irradiated disks with the latter composed of more simple ices.

Gas phase reaction kinetics of complex organic molecules at temperatures of the interstellar medium: The OH + CH3OH case

2019 ◽  
Vol 15 (S350) ◽  
pp. 35-40 ◽  
Author(s):  
André Canosa
Keyword(s):  
Interstellar Medium ◽  
Reaction Kinetics ◽  
Gas Phase ◽  
Organic Molecules ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Potential Impact ◽  
Kinetics Of ◽  
Complex Organic

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.

scholarly journals Non-thermal desorption of complex organic molecules

2019 ◽  
Vol 627 ◽  
pp. A55 ◽  
Author(s):  
E. Dartois ◽  
M. Chabot ◽  
T. Id Barkach ◽  
H. Rothard ◽  
B. Augé ◽  
...  
Keyword(s):  
Cosmic Rays ◽  
Gas Phase ◽  
Thermal Desorption ◽  
Methyl Acetate ◽  
Vacuum Ultraviolet ◽  
Organic Molecules ◽  
Bulk Composition ◽  
Water Ice ◽  
Desorption Mechanism ◽  
Complex Organic

Context. The occurrence of complex organic molecules (COMs) in the gas phase at low temperature in the dense phases of the interstellar medium suggests that a non-thermal desorption mechanism is at work because otherwise, COMs should condense within a short timescale onto dust grains. Vacuum ultraviolet (VUV) photodesorption has been shown to be much less efficient for complex organic molecules, such as methanol, because mostly photoproducts are ejected. The induced photolysis competes with photodesorption for large COMs, which considerably lowers the efficiency to desorb intact molecules. Aims. We pursue an experimental work that has already shown that water molecules, the dominant ice mantle species, can be efficiently sputtered by cosmic rays. We investigate the sputtering efficiency of complex organic molecules that are observed either in the ice mantles of interstellar dense clouds directly by infrared spectroscopy (CH3OH), or that are observed in the gas phase by millimeter telescopes (CH3COOCH3) and that could be released from interstellar grain surfaces. Methods. We irradiated ice films containing complex organic molecules (methanol and methyl acetate) and water with swift heavy ions in the electronic sputtering regime. We monitored the infrared spectra of the film as well as the species released to the gas phase with a mass spectrometer. Results. We demonstrate that when methanol or methyl acetate is embedded in a water-ice mantle exposed to cosmic rays, a large portion is sputtered as an intact molecule, with a sputtering yield close to that of the main water-ice matrix. This must be even more true for the case of more volatile ice matrices, such as those that are embedded in carbon monoxide. Conclusions. Cosmic rays penetrating deep into dense clouds provide an efficient mechanism to desorb complex organic molecules. Compared to the VUV photons, which are induced by the interaction of cosmic rays, a large portion desorb as intact molecules with a proportion corresponding to the time-dependent bulk composition of the ice mantle, the latter evolving with time as a function of fluence due to the radiolysis of the bulk.

scholarly journals Synthetic Approaches to Complex Organic Molecules in the Cold Interstellar Medium

2022 ◽  
Vol 8 ◽  
Author(s):  
Eric Herbst ◽  
Robin T. Garrod
Keyword(s):  
Low Temperature ◽  
Interstellar Medium ◽  
Gas Phase ◽  
Low Temperatures ◽  
Organic Molecules ◽  
High Energy ◽  
Interstellar Space ◽  
Interstellar Clouds ◽  
Millimeter And Submillimeter Waves ◽  
Complex Organic

The observation and synthesis of organic molecules in interstellar space is one of the most exciting and rapidly growing topics in astrochemistry. Spectroscopic observations especially with millimeter and submillimeter waves have resulted in the detection of more than 250 molecules in the interstellar clouds from which stars and planets are ultimately formed. In this review, we focus on the diverse suggestions made to explain the formation of Complex Organic Molecules (COMs) in the low-temperature interstellar medium. The dominant mechanisms at such low temperatures are still a matter of dispute, with both gas-phase and granular processes, occurring on and in ice mantles, thought to play a role. Granular mechanisms include both diffusive and nondiffusive processes. A granular explanation is strengthened by experiments at 10 K that indicate that the synthesis of large molecules on granular ice mantles under space-like conditions is exceedingly efficient, with and without external radiation. In addition, the bombardment of carbon-containing ice mantles in the laboratory by cosmic rays, which are mainly high-energy protons, can lead to organic species even at low temperatures. For processes on dust grains to be competitive at low temperatures, however, non-thermal desorption mechanisms must be invoked to explain why the organic molecules are detected in the gas phase. Although much remains to be learned, a better understanding of low-temperature organic syntheses in space will add both to our understanding of unusual chemical processes and the role of molecules in stellar evolution.

Thermal and photochemical study of CH3OH and CH3OH–O2 astrophysical ices

2020 ◽  
Vol 500 (1) ◽  
pp. 1188-1200
Author(s):  
Killian Leroux ◽  
Lahouari Krim
Keyword(s):  
Interstellar Medium ◽  
Organic Compounds ◽  
Organic Molecules ◽  
Uv Light ◽  
Hydrogen Abstraction ◽  
Insertion Reaction ◽  
Abstraction Reaction ◽  
Uv Photons ◽  
Astrophysical Ices ◽  
Complex Organic

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.

scholarly journals The formation of urea in space

2018 ◽  
Vol 610 ◽  
pp. A26 ◽  
Author(s):  
Flavio Siro Brigiano ◽  
Yannick Jeanvoine ◽  
Antonio Largo ◽  
Riccardo Spezia
Keyword(s):  
Activation Energy ◽  
Interstellar Medium ◽  
Gas Phase ◽  
Organic Molecules ◽  
Peptide Bond ◽  
Biological Molecules ◽  
Gas Phase Reactions ◽  
Molecule Reaction ◽  
Quantum Chemistry Calculations ◽  
Highly Correlated

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.

scholarly journals Laboratory data in support of JWST observations of interstellar ices

2019 ◽  
Vol 15 (S350) ◽  
pp. 420-421
Author(s):  
Marina G. Rachid ◽  
Jeroen Terwisscha van Scheltinga ◽  
Daniël Koletzki ◽  
Giulia Marcandalli ◽  
Ewine F. van Dishoeck ◽  
...  
Keyword(s):  
Solid State ◽  
Gas Phase ◽  
Organic Molecules ◽  
Methyl Formate ◽  
Laboratory Data ◽  
Protoplanetary Disks ◽  
Theoretical Studies ◽  
James Webb Space Telescope ◽  
Complex Organic ◽  
Experimental And Theoretical Studies

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

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