scholarly journals Non-thermal desorption of complex organic molecules

2020 ◽  
Vol 634 ◽  
pp. A103
Author(s):  
E. Dartois ◽  
M. Chabot ◽  
A. Bacmann ◽  
P. Boduch ◽  
A. Domaracka ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Gas Phase ◽  
Organic Molecules ◽  
Solid Phase ◽  
Bulk Composition ◽  
Cosmic Ray ◽  
Water Ice ◽  
Sputtering Yield ◽  
Sputtering Yields ◽  
Complex Organic

Aims. Methanol ice is embedded in interstellar ice mantles present in dense molecular clouds. We aim to measure the sputtering efficiencies starting from different ice mantles of varying compositions experimentally, in order to evaluate their potential impact on astrochemical models. The sputtering yields of complex organic molecules is of particular interest, since few mechanisms are efficient enough to induce a significant feedback to the gas phase. Methods. We irradiated ice film mixtures made of methanol and carbon dioxide of varying ratios with swift heavy ions in the electronic sputtering regime. We monitored the evolution of the infrared spectra as well as the species released to the gas phase with a mass spectrometer. Methanol (12C) and isotopically labelled 13C-methanol were used to remove any ambiguity on the measured irradiation products. Results. The sputtering of methanol embedded in carbon dioxide ice is an efficient process leading to the ejection of intact methanol in the gas phase. We establish that when methanol is embedded in a carbon-dioxide-rich mantle exposed to cosmic rays, a significant fraction (0.2–0.3 in this work) is sputtered as intact molecules. The sputtered fraction follows the time-dependent bulk composition of the ice mantle, the latter evolving with time due to the radiolysis-induced evolution of the bulk. If methanol is embedded in a carbon dioxide ice matrix, as the analyses of the spectral shape of the CO2 bending mode observations in some lines of sight suggest, the overall methanol sputtering yield is higher than if embedded in a water ice mantle. The sputtering is increased by a factor close to the dominant ice matrix sputtering yield, which is about six times higher for pure carbon dioxide ice when compared to water ice. These experiments are further constraining the cosmic-ray-induced ice mantle sputtering mechanisms important role in the gas-phase release of complex organic molecules from the interstellar solid phase.

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 The role of radiolysis in the modelling of C2H4O2 isomers and dimethyl ether in cold dark clouds

2020 ◽  
Vol 500 (3) ◽  
pp. 3414-3424
Author(s):  
Alec Paulive ◽  
Christopher N Shingledecker ◽  
Eric Herbst
Keyword(s):  
Gas Phase ◽  
Dimethyl Ether ◽  
Recent Observation ◽  
Cosmic Ray ◽  
Thermal Method ◽  
Dark Clouds ◽  
Ice Surface ◽  
Dust Grain ◽  
Complex Organic

ABSTRACT Complex organic molecules (COMs) have been detected in a variety of interstellar sources. The abundances of these COMs in warming sources can be explained by syntheses linked to increasing temperatures and densities, allowing quasi-thermal chemical reactions to occur rapidly enough to produce observable amounts of COMs, both in the gas phase, and upon dust grain ice mantles. The COMs produced on grains then become gaseous as the temperature increases sufficiently to allow their thermal desorption. The recent observation of gaseous COMs in cold sources has not been fully explained by these gas-phase and dust grain production routes. Radiolysis chemistry is a possible non-thermal method of producing COMs in cold dark clouds. This new method greatly increases the modelled abundance of selected COMs upon the ice surface and within the ice mantle due to excitation and ionization events from cosmic ray bombardment. We examine the effect of radiolysis on three C2H4O2 isomers – methyl formate (HCOOCH3), glycolaldehyde (HCOCH2OH), and acetic acid (CH3COOH) – and a chemically similar molecule, dimethyl ether (CH3OCH3), in cold dark clouds. We then compare our modelled gaseous abundances with observed abundances in TMC-1, L1689B, and B1-b.

Photon and thermal processing of CH3NH2-bearing ices. Synthesis of prebiotic species at low temperature (such as formamide, ethylamine, and methylcyanide), and N-heterocycles during warm up.

2021 ◽  
Author(s):  
Héctor Carrascosa ◽  
Cristóbal González Díaz ◽  
Guillermo M. Muñoz Caro ◽  
Pedro C. Gómez ◽  
María Luz Sanz
Keyword(s):  
Vacuum Chamber ◽  
Organic Molecules ◽  
Solid Phase ◽  
High Vacuum ◽  
Ultra High Vacuum ◽  
Quadrupole Mass ◽  
Warm Up ◽  
Methyl Cyanide ◽  
Interstellar Ice ◽  
Complex Organic

<p>Hexamethylentetramine has drawn a lot of attention due to its potential to produce prebiotic species. This work aims to gain a better understanding in the chemical processes concerning methylamine under astrophysically relevant conditions. In particular, this work deeps into the formation of N-heterocycles in interstellar ice analogs exposed to UV radiation, which may lead to the formation of prebiotic species.</p> <p>Experimental simulations of interstellar ice analogs were carried out in ISAC. ISAC is an ultra-high vacuum chamber equipped with a cryostat, where gas and vapour species are frozen forming ice samples. Infrared and ultraviolet spectroscopy were used to monitor the solid phase, and quadrupole mass spectrometry served to measure the composition of the gas phase. The variety of species detected after UV irradiation of ices containing  methylamine revealed the presence of 12 species which have been already detected in the ISM, being 4 of them typically classified as complex organic molecules: formamide (HCONH<sub>2</sub>), methyl cyanide (CH<sub>3</sub>CN), CH<sub>3</sub>NH and CH<sub>3</sub>CHNH. Warming up of the irradiated CH<sub>3</sub>NH<sub>2</sub>-bearing ice samples lead to the formation of trimethylentriamine (TMT), a N-heterocycle precursor of HMT, and the subsequent synthesis of HMT at temperatures above 230 K.</p>

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.

scholarly journals Infrared spectra of complex organic molecules in astronomically relevant ice matrices

2018 ◽  
Vol 611 ◽  
pp. A35 ◽  
Author(s):  
J. Terwisscha van Scheltinga ◽  
N. F. W. Ligterink ◽  
A. C. A. Boogert ◽  
E. F. van Dishoeck ◽  
H. Linnartz
Keyword(s):  
Gas Phase ◽  
Dimethyl Ether ◽  
Organic Molecules ◽  
Laboratory Data ◽  
Laboratory Studies ◽  
Astronomical Data ◽  
Astronomical Observations ◽  
Circumstellar Gas ◽  
Complex Organic ◽  
Recent Laboratory

Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking.Aim. This work provides infrared reference spectra of acetaldehyde (CH3CHO), ethanol (CH3CH2OH), and dimethyl ether (CH3OCH3) recorded in a variety of ice environments and for astronomically relevant temperatures, as needed to guide or interpret astronomical observations, specifically for upcoming James Webb Space Telescope observations.Methods. Fourier transform transmission spectroscopy (500–4000 cm−1/20–2.5 μm, 1.0 cm−1 resolution) was used to investigate solid acetaldehyde, ethanol and dimethyl ether, pure or mixed with water, CO, methanol, or CO:methanol. These species were deposited on a cryogenically cooled infrared transmissive window at 15 K. A heating ramp was applied, during which IR spectra were recorded until all ice constituents were thermally desorbed.Results. We present a large number of reference spectra that can be compared with astronomical data. Accurate band positions and band widths are provided for the studied ice mixtures and temperatures. Special efforts have been put into those bands of each molecule that are best suited for identification. For acetaldehyde the 7.427 and 5.803 μm bands are recommended, for ethanol the 11.36 and 7.240 μm bands are good candidates, and for dimethyl ether bands at 9.141 and 8.011 μm can be used. All spectra are publicly available in the Leiden Database for Ice.

scholarly journals A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules

2016 ◽  
Vol 113 (28) ◽  
pp. 7727-7732 ◽  
Author(s):  
Matthew J. Abplanalp ◽  
Samer Gozem ◽  
Anna I. Krylov ◽  
Christopher N. Shingledecker ◽  
Eric Herbst ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Cosmic Ray ◽  
Formation Mechanisms ◽  
Molecular Precursors ◽  
Star Forming ◽  
Star Forming Regions ◽  
Interstellar Ices ◽  
A Chain ◽  
Nonequilibrium Chemistry ◽  
Complex Organic

Complex organic molecules such as sugars and amides are ubiquitous in star- and planet-forming regions, but their formation mechanisms have remained largely elusive until now. Here we show in a combined experimental, computational, and astrochemical modeling study that interstellar aldehydes and enols like acetaldehyde (CH3CHO) and vinyl alcohol (C2H3OH) act as key tracers of a cosmic-ray-driven nonequilibrium chemistry leading to complex organics even deep within low-temperature interstellar ices at 10 K. Our findings challenge conventional wisdom and define a hitherto poorly characterized reaction class forming complex organic molecules inside interstellar ices before their sublimation in star-forming regions such as SgrB2(N). These processes are of vital importance in initiating a chain of chemical reactions leading eventually to the molecular precursors of biorelevant molecules as planets form in their interstellar nurseries.

scholarly journals Dust and molecules in extra-galactic planetary nebulae

2015 ◽  
Vol 11 (A29B) ◽  
Author(s):  
D. A. García-Hernández
Keyword(s):  
Solid State ◽  
Gas Phase ◽  
Organic Molecules ◽  
Local Group ◽  
Planetary Nebulae ◽  
Circumstellar Envelopes ◽  
The Galaxy ◽  
Models Comparison ◽  
Polycyclic Aromatic ◽  
Complex Organic

AbstractExtra-galactic planetary nebulae (PNe) permit the study of dust and molecules in metallicity environments other than the Galaxy. Their known distances lower the number of free parameters in the observations vs. models comparison, providing strong constraints on the gas-phase and solid-state astrochemistry models. Observations of PNe in the Galaxy and other Local Group galaxies such as the Magellanic Clouds (MC) provide evidence that metallicity affects the production of dust as well as the formation of complex organic molecules and inorganic solid-state compounds in their circumstellar envelopes. In particular, the lower metallicity MC environments seem to be less favorable to dust production and the frequency of carbonaceous dust features and complex fullerene molecules is generally higher with decreasing metallicity. Here, I present an observational review of the dust and molecular content in extra-galactic PNe as compared to their higher metallicity Galactic counterparts. A special attention is given to the level of dust processing and the formation of complex organic molecules (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene precursors) depending on metallicity.

scholarly journals Infrared spectra of complex organic molecules in astronomically relevant ice mixtures

2020 ◽  
Vol 639 ◽  
pp. A4
Author(s):  
M. G. Rachid ◽  
J. Terwisscha van Scheltinga ◽  
D. Koletzki ◽  
H. Linnartz
Keyword(s):  
Ir Spectra ◽  
Infrared Spectra ◽  
Organic Molecules ◽  
Solid Phase ◽  
High Vacuum ◽  
Peak Position ◽  
Large Set ◽  
Complex Species ◽  
Asymmetric Stretch ◽  
Complex Organic

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

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.

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