Formation Of Complex Organic Molecules Research Articles

Predicting products of space ice chemistry

In the search for sources of complex organic molecules in space, some researchers have turned to hydrocarbon ices, which exist in interstellar space and on bodies in our solar system, such as Saturn’s moon Titan. Experiments have shown that high-energy electrons generated by ionizing radiation can induce formation of complex organic molecules on these ices. However, researchers still aren’t sure which chemicals form inside of the ices and which form on their surface or in nearby gases. Existing models of space chemistry can’t predict the products of such reactions. At the ACS meeting last week, researchers reported that they used tunable lasers to identify which isomers of small hydrocarbon molecules form within methane ice in laboratory experiments simulating interstellar conditions. Matthew Abplanalp, a graduate student in Ralf I. Kaiser’s group at University of Hawaii, Manoa, and colleagues held methane ice at 5.5 K inside an ultrahigh vacuum, bombarded it with

A Multiline Study of a High-mass Young Stellar Object in the Small Magellanic Cloud with ALMA: The Detection of Methanol Gas at 0.2 Solar Metallicity

We report the results of subparsec-scale submillimeter observations towards an embedded high-mass young stellar object in the Small Magellanic Cloud (SMC) with ALMA. Complementary infrared data obtained with the AKARI satellite and the Gemini South telescope are also presented. The target infrared point source is spatially resolved into two dense molecular cloud cores; one is associated with a high-mass young stellar object (YSO core), while another is not associated with an infrared source (East core). The two cores are dynamically associated but show different chemical characteristics. Emission lines of CS, C33S, H2CS, SO, SO2, CH3OH, H13CO+, H13CN, SiO, and dust continuum are detected from the observed region. Tentative detection of HDS is also reported. The first detection of CH3OH in the SMC has a strong impact on our understanding of the formation of complex organic molecules in metal-poor environments. The gas temperature is estimated to be ~10 K based on the rotation analysis of CH3OH lines. The fractional abundance of CH3OH gas in the East core is estimated to be (0.5-1.5) x 10^(-8), which is comparable with or marginally higher than those of similar cold sources in our Galaxy despite a factor of five lower metallicity in the SMC. This work provides observational evidence that an organic molecule like CH3OH, which is largely formed on grain surfaces, can be produced even in a significantly lower metallicity environment compared to the solar neighborhood. A possible origin of cold CH3OH gas in the observed dense core is discussed.

On Cosmic-Ray-driven Grain Chemistry in Cold Core Models

Abstract In this paper, we present preliminary results illustrating the effect of cosmic rays on solid-phase chemistry in models of both TMC-1 and several sources with physical conditions identical to TMC-1 except for hypothetically enhanced ionization rates. Using a recent theory for the addition of cosmic-ray-induced reactions to astrochemical models, we calculated the radiochemical yields, called G values, for the primary dust grain ice-mantle constituents. We show that the inclusion of this nonthermal chemistry can lead to the formation of complex organic molecules from simpler ice-mantle constituents, even under cold core conditions. In addition to enriching ice mantles, we find that these new radiation-chemical processes can lead to increased gas-phase abundances as well, particularly for HOCO, NO2, HC2O, methyl formate (HCOOCH3), and ethanol (CH3CH2OH). These model results imply that HOCO—and perhaps NO2—might be observable in TMC-1. Future detections of either of these two species in cold interstellar environments could provide strong support for the importance of cosmic-ray-driven radiation chemistry. The increased gas-phase abundance of methyl formate can be compared with abundances achieved through other formation mechanisms such as pure gas-phase chemistry and surface reactions.

Hydrogen transfer reactions of interstellar complex organic molecules

Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in ices rich in carbon monoxide (CO) in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate, and an additional three reactions where |${\rm CH}_n{\mathrm{ O}}$| fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore, the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g. breaking or forming a C–C or C–O bond, have rate constants that are much lower than those where H transfer is involved.

TileViz : Tile visualization for direct dynamics applied to astrochemical reactions.

We present a small multiples approach to analyze an ensemble of molecular dynamics trajectories related to reactions of astrochemical interest. A tiled visualization tool is being developed on the M<small>ANDELBROT</small> platform housed at Maison de la Simulation in Saclay (France). Instead of one huge screen, the TileViz software allows to present every visualization tool outputs side by side. Scientists are able to analyze multiple simulations at the same time, with varied parameters, or to visually compare similar results. We have included in our tool the VMD molecular dynamics viewer, making it useful for the broad molecular dynamics community. Here, as a case study, we applied the approach to chemical dynamics trajectories performed by some of us with the aim of understanding possible synthetic pathways for the formation of complex organic molecules in space.

Reduction of C[double bond, length as m-dash]O functional groups through H addition reactions: a comparative study between H2CO + H, CH3CH2CHO + H and CH3OCHO + H under interstellar conditions.

H-addition reactions on the icy interstellar grains may play an important role in the formation of complex organic molecules. In the present work we propose a comparative study of H2CO + H, CH3CH2CHO + H and CH3OCHO + H solid state reactions at 10 K under interstellar conditions in order to characterize the main reaction pathways involved in the hydrogenation of a CHO functional group. We show that the most probable mechanism for the formation of alcohols under non-energetic conditions through the saturation of the CHO group corresponds to the attachment of the H atom to the CH group with noticeable variations of the energy barriers for each studied reaction. These energy barriers have been calculated to be 8.3, 14.6 and 32.7 kJ mol-1 for H2CO + H, CH3CH2CHO + H and CH3OCHO + H, respectively. The coupling of the experimental and theoretical analysis proves that while the simplest aldehyde, formaldehyde, is easily reduced to methanol, methylformate and propanal behave differently under H-bombardments but they cannot be a source of alcohol formation through H-addition reactions. Consequently, for the formation of alcohols larger than CH3OH, other chemical pathways should be taken into account, probably energetic processing such as the photolysis of interstellar ice analogues containing C-, H- and O-bearing compounds or the coupling of the H-addition reaction and photon-irradiation on species with a CHO functional group.

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

Abstract Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir–Hinshelwood and the Eley–Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ∼80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

Low-temperature Condensation of Carbon

Abstract Two different types of experiments were performed. In the first experiment, we studied the low-temperature condensation of vaporized graphite inside bulk liquid helium, while in the second experiment, we studied the condensation of single carbon atoms together with H2, H2O, and CO molecules inside helium nanodroplets. The condensation of vaporized graphite leads to the formation of partially graphitized carbon, which indicates high temperatures, supposedly higher than 1000°C, during condensation. Possible underlying processes responsible for the instant rise in temperature during condensation are discussed. This suggests that such processes cause the presence of partially graphitized carbon dust formed by low-temperature condensation in the diffuse interstellar medium. Alternatively, in the denser regions of the ISM, the condensation of carbon atoms together with the most abundant interstellar molecules (H2, H2O, and CO), leads to the formation of complex organic molecules (COMs) and finally organic polymers. Water molecules were found not to be involved directly in the reaction network leading to the formation of COMs. It was proposed that COMs are formed via the addition of carbon atoms to H2 and CO molecules . Due to the involvement of molecular hydrogen, the formation of COMs by carbon addition reactions should be more efficient at high extinctions compared with the previously proposed reaction scheme with atomic hydrogen.

A theoretical quantum chemical study of alanine formation in interstellar medium

The interstellar medium, the vast space between the stars, is a rich reservoir of molecular material ranging from simple diatomic molecules to more complex, astrobiologically important molecules such as amino acids, nucleobases, and other organic species. Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low temperature chemistry. An attempt has been made to explore the possibility of formation of complex organic molecules in interstellar medium, through detected interstellar molecules like CH3CN and HCOOH. The gas phase reactions are theoretically studied using quantum chemical techniques. We used the density functional theory (DFT) at the B3LYP/6-311G(d, p) level. The reaction energies, potential barrier and optimized structures of all the geometries, involved in the reaction path, has been discussed. We report the potential energy surfaces for the reactions considered in this work.

Complex organic molecules in strongly UV-irradiated gas.

We investigate the presence of complex organic molecules (COMs) in strongly UV-irradiated interstellar molecular gas. We have carried out a complete millimetre (mm) line survey using the IRAM 30 m telescope towards the edge of the Orion Bar photodissociation region (PDR), close to the H2 dissociation front, a position irradiated by a very intense far-UV (FUV) radiation field. These observations have been complemented with 8.5″ resolution maps of the H2CO JKa,Kc = 51,5 → 41,4 and C18O J = 3 → 2 emission at 0.9 mm. Despite being a harsh environment, we detect more than 250 lines from COMs and related precursors: H2CO, CH3OH, HCO, H2CCO, CH3CHO, H2CS, HCOOH, CH3CN, CH2NH, HNCO, [Formula: see text] and HC3N (in decreasing order of abundance). For each species, the large number of detected lines allowed us to accurately constrain their rotational temperatures (Trot) and column densities (N). Owing to subthermal excitation and intricate spectroscopy of some COMs (symmetric- and asymmetric-top molecules such as CH3CN and H2CO, respectively), a correct determination of N and Trot requires building rotational population diagrams of their rotational ladders separately. The inferred column densities are in the 1011 - 1013cm-2 range. We also provide accurate upper limit abundances for chemically related molecules that might have been expected, but are not conclusively detected at the edge of the PDR (HDCO, CH3O, CH3NC, CH3CCH, CH3OCH3, HCOOCH3, CH3CH2OH, CH3CH2CN, and CH2CHCN). A non-thermodynamic equilibrium excitation analysis for molecules with known collisional rate coefficients suggests that some COMs arise from different PDR layers but we cannot resolve them spatially. In particular, H2CO and CH3CN survive in the extended gas directly exposed to the strong FUV flux (Tk = 150 - 250 K and Td ≳ 60 K), whereas CH3OH only arises from denser and cooler gas clumps in the more shielded PDR interior (Tk = 40 - 50 K). The non-detection of HDCO towards the PDR edge is consistent with the minor role of pure gas-phase deuteration at very high temperatures. We find a HCO/H2CO/CH3OH ≃ 1/5/3 abundance ratio. These ratios are different from those inferred in hot cores and shocks. Taking into account the elevated gas and dust temperatures at the edge of the Bar (mostly mantle-free grains), we suggest the following scenarios for the formation of COMs: (i) hot gas-phase reactions not included in current models; (ii) warm grain-surface chemistry; or (iii) the PDR dynamics is such that COMs or precursors formed in cold icy grains deeper inside the molecular cloud desorb and advect into the PDR.

Complex Organic Molecules Formation in Space Through Gas Phase Reactions: A Theoretical Approach

Abstract Chemistry in the interstellar medium (ISM) is capable of producing complex organic molecules (COMs) of great importance to astrobiology. Gas phase and grain surface chemistry almost certainly both contribute to COM formation. Amino acids as building blocks of proteins are some of the most interesting COMs. The simplest one, glycine, has been characterized in meteorites and comets and, its conclusive detection in the ISM seems to be highly plausible. In this work, we analyze the gas phase reaction of glycine and to establish the role of this process in the formation of alanine or other COMs in the ISM. Formation of protonated α- and β-alanine in spite of being exothermic processes is not viable under interstellar conditions because the different paths leading to these isomers present net activation energies. Nevertheless, glycine can evolve to protonated 1-imide-2, 2-propanediol, protonated amino acetone, protonated hydroxyacetone, and protonated propionic acid. However, formation of acetic acid and protonated methylamine is also a favorable process and therefore will be a competitive channel with the evolution of glycine to COMs.

Binding energies: New values and impact on the efficiency of chemical desorption

Recent laboratory measurements have confirmed that chemical desorption (desorption of products due to exothermic surface reactions) can be an efficient process. The impact of including this process into gas-grain chemical models entirely depends on the formalism used and the associated parameters. Among these parameters, binding energies are probably the most uncertain ones for the moment. We propose a new model to compute binding energy of species to water ice surfaces. We have also compared the model results using either the new chemical desorption model proposed by Minissale et al. (2016) or the one of Garrod et al. (2007). The new binding energies have a strong impact on the formation of complex organic molecules. In addition, the new chemical desorption model from Minissale produces a much smaller desorption of these species and also of methanol. Combining the two effects, the abundances of CH3OH and COMs observed in cold cores cannot be reproduced by astrochemical models anymore.

The Spatial Distribution of Complex Organic Molecules in the L1544 Pre-stellar Core.

The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T<10 K), has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modelling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly-extinguished continuum peak with A V ≥30 mag within the inner 2700 au; and a low-density shell with average A V ~7.5-8 mag located at 4000 au from the core's center and bright in CH3OH. Our observations show that CH3O, CH3OCH3 and CH3CHO are more abundant (by factors ~2-10) toward the low-density shell than toward the continuum peak. Other COMs such as CH3OCHO, c-C3H2O, HCCCHO, CH2CHCN and HCCNC show slight enhancements (by factors ≤3) but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modelling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because i) CO starts freezing out onto dust grains driving an active surface chemistry; ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and iii) the density is still moderate to prevent severe depletion of COMs onto grains.

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules – glycolaldehyde, ethylene glycol, and polyoxymethylene – through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2 CO proceed preferentially through CH2 OH intermediate radicals rather than the CH3 O radical.

PROBING PLANET FORMING ZONES WITH RARE CO ISOTOPOLOGUES

ABSTRACT The gas near the midplanes of planet-forming protostellar disks remains largely unprobed by observations due to the high optical depth of commonly observed molecules such as CO and H2O. However, rotational emission lines from rare molecules may have optical depths near unity in the vertical direction, so that the lines are strong enough to be detected, yet remain transparent enough to trace the disk midplane. Here we present a chemical model of an evolving T Tauri disk and predict the optical depths of rotational transitions of 12C16O, 13C16O, 12C17O, and 12C18O. The MRI-active disk is primarily heated by the central star due to the formation of the dead zone. CO does not freeze out in our modeled region within around a sunlike star. However, the abundance of CO decreases because of the formation of complex organic molecules, producing an effect that can be misinterpreted as the “snow line.” These results are robust to variations in our assumptions about the evolution of the gas-to-dust ratio. The optical depths of low-order rotational lines of C17O are around unity, making it possible to see into the disk midplane using C17O. Combining observations with modeled C17O/H2 ratios, like those we provide, can yield estimates of protoplanetary disks’ gas masses.

FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

ABSTRACT During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

UNIFIED MICROSCOPIC–MACROSCOPIC MONTE CARLO SIMULATIONS OF COMPLEX ORGANIC MOLECULE CHEMISTRY IN COLD CORES

ABSTRACT The recent discovery of methyl formate and dimethyl ether in the gas phase of cold cores with temperatures as cold as 10 K challenges our previous astrochemical models concerning the formation of complex organic molecules (COMs). The strong correlation between the abundances and distributions of methyl formate and dimethyl ether further shows that current astrochemical models may be missing important chemical processes in cold astronomical sources. We investigate a scenario in which COMs and the methoxy radical can be formed on dust grains via a so-called chain reaction mechanism, in a similar manner to CO2. A unified gas-grain microscopic–macroscopic Monte Carlo approach with both normal and interstitial sites for icy grain mantles is used to perform the chemical simulations. Reactive desorption with varying degrees of efficiency is included to enhance the nonthermal desorption of species formed on cold dust grains. In addition, varying degrees of efficiency for the surface formation of methoxy are also included. The observed abundances of a variety of organic molecules in cold cores can be reproduced in our models. The strong correlation between the abundances of methyl formate and dimethyl ether in cold cores can also be explained. Nondiffusive chemical reactions on dust grain surfaces may play a key role in the formation of some COMs.

VLT/ISAAC infrared spectroscopy of embedded high-mass YSOs in the Large Magellanic Cloud: Methanol and the 3.47μm band

This study aims to elucidate a possible link between chemical properties of ices in star-forming regions and environmental characteristics of the host galaxy. We performed 3--4 micron spectroscopic observations toward nine embedded high-mass YSOs in the Large Magellanic Cloud (LMC) with the ISAAC at the VLT. Additionally, we analyzed archival ISAAC data of two LMC YSOs. As a result, we detected absorption bands due to solid H2O and CH3OH as well as the 3.47 micron absorption band. The 3.53 micron CH3OH ice absorption band for the LMC YSOs is found to be absent or very weak compared to that seen toward Galactic sources. The result suggests the low abundance of CH3OH ice in the LMC. The 3.47 micron absorption band is detected toward six out of eleven LMC YSOs. We found that the 3.47 micron band and the H2O ice band correlate similarly between the LMC and Galactic samples, but the LMC sources seem to require a slightly higher H2O ice threshold for the appearance of the 3.47 micron band. For the LMC sources with relatively large H2O ice optical depths, we found that the strength ratio of the 3.47 micron band relative to the water ice band is only marginally lower than those of the Galactic sources. We propose that grain surface reactions at a relatively high dust temperature (warm ice chemistry) are responsible for the observed characteristics of ice chemical compositions in the LMC. We suggest that this warm ice chemistry is one of the important characteristics of interstellar and circumstellar chemistry in low metallicity environments. The low abundance of CH3OH in the solid phase implies that formation of complex organic molecules from methanol-derived species is less efficient in the LMC. For the 3.47 micron band, the observed difference in the water ice threshold may suggest that a more shielded environment is necessary for the formation of the 3.47 micron band carrier in the LMC.

Dust and molecules in extra-galactic planetary nebulae

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.

Astrochemistry at work in the L1157-B1 shock: acetaldehyde formation

Abstract The formation of complex organic molecules (COMs) in protostellar environments is a hotly debated topic. In particular, the relative importance of the gas phase processes as compared to a direct formation of COMs on the dust grain surfaces is so far unknown. We report here the first high-resolution images of acetaldehyde (CH3CHO) emission towards the chemically rich protostellar shock L1157-B1, obtained at 2 mm with the IRAM Plateau de Bure interferometer. Six blueshifted CH3CHO lines with Eu = 26–35 K have been detected. The acetaldehyde spatial distribution follows the young (∼ 2000 yr) outflow cavity produced by the impact of the jet with the ambient medium, indicating that this COM is closely associated with the region enriched by iced species evaporated from dust mantles and released into the gas phase. A high CH3CHO relative abundance, 2–3 × 10−8, is inferred, similarly to what found in hot corinos. Astrochemical modelling indicates that gas phase reactions can produce the observed quantity of acetaldehyde only if a large fraction of carbon, of the order of 0.1 per cent, is locked into iced hydrocarbons.