Formation Of Complex Organic Molecules Research Articles

Monte Carlo simulation of UV-driven synthesis of complex organic molecules on icy grain surfaces

Complex organic molecules (COMs) have been widely observed in molecular clouds and protostellar environments. One of the formation mechanisms of COMs is radical reactions on the icy grain surface driven by UV irradiation. While many experiments have reported that various COMs (including biomolecules) can be synthesized under such ice conditions, the majority of the reaction processes are unclear. Complementary numerical simulations are necessary to unveil the synthetic process behind the formation of COMs. In this study, we develop a chemical reaction simulation using a Monte Carlo method. To explore the complex reaction network of COM synthesis, the model was designed to eliminate the need to prepare reaction pathways in advance and to keep computational costs low. This allows for broad parameter surveys and a global investigation of COM synthesis reactions. With this simulation, we investigate the chemical reactions occurring on icy dust surfaces during and after UV irradiation, assuming a protoplanetary disk environment. We aim to reveal the types of organic molecules produced in a disk and the formation mechanisms of COMs, in particular, amino acids and sugars. The Monte Carlo method we developed here produces reaction sequences by selecting a reaction from all candidate reactions at each calculation step, based on Arrhenius-type weighting. For our purpose, we significantly accelerated the calculation by adopting an approximate estimation of activation energy without expensive quantum chemical calculations. The results show that photodissociation and subsequent radical-radical reactions cause random rearrangement of the covalent bonds in the initial molecules composed of methanol, formaldehyde, ammonia, and water. Consequently, highly complex molecules such as amino acids and sugars were produced in a wide range of the initial conditions. We found that the final abundances of amino acids and sugars have extremely similar dependence on the atomic ratios of the initial molecules, which peak at $ C/H 0.1$-0.3 and $ O/H 0.3$-0.5, although the amino acids abundance is usually more than ten times higher than that of sugars. To understand this dependence, a semi-analytical formula was derived. Additionally, parameter surveys of temperature, photon energy, and other factors have suggested that the decomposition reactions of amino acids and sugars undergo a rapid transition within the threshold of a given parameter.

Formation of N--bearing complex organic molecules in molecular clouds: Ketenimine, acetonitrile, acetaldimine, and vinylamine via the UV photolysis of C_2H_2 ice

The solid-state C$_2$H$_2$ chemistry in interstellar H$_2$O-rich ice has been proposed to explain astronomically observed complex organic molecules (COMs), including ketene (CH$_2$CO), acetaldehyde (CH$_3$CHO), and ethanol (CH$_3$CH$_2$OH), toward early star-forming regions. This formation mechanism is supported by recent laboratory studies and theoretical calculations for the reactions of C$_2$H$_2$+OH/H. However, the analog reaction of C$_2$H$_2$+NH$_2$ forming N-bearing species has been suggested to have a relatively low rate constant that is orders of magnitude lower than the value of C$_2$H$_2$+OH. This work extends our previous laboratory studies on O-bearing COM formation to investigate the interactions between C$_2$H$_2$ and NH$_3$ ice triggered by cosmic ray-induced secondary UV photons under molecular cloud conditions. Experiments were performed in an ultra-high vacuum chamber to investigate the UV photolysis of the C$_2$H$_2$:NH$_3$ ice mixture at 10 K. The ongoing chemistry was monitored in situ by Fourier-transform infrared spectroscopy as a function of photon fluence. The IR spectral identification of the newly formed N-bearing products was further secured by a quadrupole mass spectrometer during the temperature-programmed desorption experiment. The studied ice chemistry of C$_2$H$_2$ with NH$_2$ radicals and H atoms resulting from the UV photodissociation of NH$_3$ leads to the formation of several N-bearing COMs, including vinylamine (CH$_2$CHNH$_2$), acetaldimine (CH$_3$CHNH), acetonitrile (CH$_3$CN), ketenimine (CH$_2$CNH), and tentatively ethylamine (CH$_3$CH$_2$NH$_2$). The experimental results show an immediate and abundant CH$_2$CHNH$_2$ yield as the first-generation product, which is further converted into other chemical derivatives. The effective destruction and formation cross-section values of parent species and COMs were derived, and we discuss the chemical links among these molecules and their astronomical relevance.

Formation pathways of formic acid (HCOOH) in regions with methanol ices

We modeled the collisions between OH^+ projectiles with kinetic energies ranging from 10 to 22 eV and an amorphous cold (CH3OH)_10 substrate using Born-Oppenheimer molecular dynamics (BOMD) simulations. We conducted the simulations for a collision time of 400 femtoseconds (fs), during which we followed multiple bond-forming and breaking reactions. Here, we report four new pathways for the formation of formic acid HCOOH . We find new precursors such as CH3(OH)2+ HC(OH)2^+ CH2OH^+ and CH2(OH)2 which are essential in these pathways for the formation of formic acid. The methanodiol CH2(OH)2 and hydroxymethyl CH2OH^+ cations have previously been identified as key precursors of formaldehyde. These pathways suggest new ways to form formic acid in methanol ice mantles on dust grains, offering alternative mechanisms leading to the formation of complex organic molecules (COMs) in space.

Water molecule elimination from the protonated methanol dimer ion-An example of a size-selective intracluster reaction.

The abundance of extraterrestrial methanol makes the reaction between methanol molecules in a molecular cluster a possible key step in the search for mechanisms for the formation of more complex molecules under the conditions of the interstellar medium as well as circumstellar and planetary atmospheres. The reaction leading to the formation of the dimethyl ether ion from a methanol molecule interacting with a protonated methanol ion via the elimination of a water molecule is a basic mechanism for the formation of complex organic molecules. Here, we experimentally examine such reactions in the gas phase, analyzing the production and reactivity of protonated cluster ions formed by the ionization of a supersonic jet of methanol. Focusing especially on the post-collisional relaxation of the protonated methanol dimer and trimer ions after high-energy single collisions, the results indicate a strong size selectivity favoring the occurrence of this reaction only in the dimer ion. To elucidate this behavior, the velocity distribution of the eliminated water molecule was measured using an event-by-event coincidence analysis. These results are interpreted using quantum chemical calculations of the dissociation pathways. It turns out that in the dimer case, two transition states are able to contribute to this intracluster reaction. In the trimer case, methanol evaporation appears as the most energetically favorable relaxation pathway.

Dust and Ice in the Interstellar Medium

In this paper, we present an introduction to bare dust particles and grains covered by ice sheets in diffuse and dense interstellar clouds. It follows the life cycle of dust from its formation in stellar environments to its incorporation into the body of the Solar system. Dust particles play an important role in the physics and chemistry of many space environments. Regarding dust composition, two different populations are generally observed: silicate and carbonaceous dust. Energetic processing of ice layers with UV rays, X – rays or cosmic rays, after which the heat leads to the formation of complex organic molecules; some of them have prebiotic properties. Delivery of this organic fraction to the early Earth by meteorites and asteroids may have contributed to the origin of life.

Organic Chemistry in the H2-bearing, CO-rich Interstellar Ice Layer at Temperatures Relevant to Dense Cloud Interiors

Ice chemistry in the dense, cold interstellar medium (ISM) is probably responsible for the formation of interstellar complex organic molecules (COMs). Recent laboratory experiments performed at T ∼ 4 K have shown that irradiation of CO:N2 ice samples analog to the CO-rich interstellar ice layer can contribute to the formation of COMs when H2 molecules are present. We have tested this organic chemistry under a broader range of conditions relevant to the interior of dense clouds by irradiating CO:15N2:H2 ice samples with 2 keV electrons in the 4–15 K temperature range. The H2 ice abundance depended on both, the ice formation temperature and the thermal evolution of the samples. Formation of H-bearing organics such as formaldehyde (H2CO), ketene (C2H2O), and isocyanic acid (H15NCO) was observed upon irradiation of ice samples formed at temperatures up to 10 K, and also in ices formed at 6 K and subsequently warmed up and irradiated at temperatures up to 15 K. These results suggest that a fraction of the H2 molecules in dense cloud interiors might be entrapped in the CO-rich layer of interstellar ice mantles, and that energetic processing of this layer could entail an additional contribution to the formation of COMs in the coldest regions of the ISM.

Chemistry of Complex Organic Molecules in the V883 Ori Disk Revealed by ALMA Band 3 Observations

Complex organic molecules (COMs) in protoplanetary disks are key to understanding the origin of volatiles in comets in our solar system, yet the chemistry of COMs in protoplanetary disks remains poorly understood. Here, we present Atacama Large Millimeter/submillimeter Array Band 3 observations of the disk around the young outbursting star V883 Ori, where the COMs sublimate from ices and are thus observable thanks to the warm condition of the disk. We have robustly identified ten oxygen-bearing COMs including 13C isotopologues in the disk-integrated spectra. The radial distributions of the COM emission, revealed by the detailed analyses of the line profiles, show the inner emission cavity, similar to the previous observations in Band 6 and Band 7. We found that the COMs abundance ratios with respect to methanol are significantly higher than those in the warm protostellar envelopes of IRAS 16293-2422 and similar to the ratios in the solar system comet 67P/Churyumov-Gerasimenko, suggesting the efficient (re)formation of COMs in protoplanetary disks. We also constrained the 12C/13C and D/H ratios of COMs in protoplanetary disks for the first time. The 12C/13C ratios of acetaldehyde, methyl formate, and dimethyl ether are consistently lower (∼20–30) than the canonical ratio in the interstellar medium (∼69), indicating the efficient 13C-fractionation of CO. The D/H ratios of methyl formate are slightly lower than the values in IRAS 16293-2422, possibly pointing to the destruction and reformation of COMs in disks. We also discuss the implications for nitrogen and sulfur chemistry in protoplanetary disks.

Bridging the gap: viable reaction pathways from tetrahedrane to benzyne.

The addition of sp-carbon-containing molecules to polycyclic sp3 tetrahedrane (c-C4H4) results in the formation of both o-benzyne (c-C6H4) and benzene (c-C6H6). Since both c-C6H4 and c-C6H6 have been detected in the interstellar medium (ISM), providing additional pathways for their possible astrochemical formation mechanisms can lead to the discovery of other molecules, such as c-C4H4, benzvalyne, and vinylidene (:CCH2). Addition of diatomic carbon (C2), the ethynyl radical (C2H), vinylidene, and acetylene (HCCH) to c-C4H4 is undertaken in individual pathways through high-level quantum chemical computations at the CCSD(T)-F12b/cc-pVTZ-F12 level of theory. The resulting C2 addition pathway proceeds barrierlessly through benzvalyne as an intermediate and reaches a true minimum at c-C6H4, but no leaving groups are produced which is required to dissipate excess energy within an interstellar chemical scheme. Similarly, the C2H addition to c-C4H4 produces benzvalyne as well as its related isomers. This pathway allows for the loss of a hydrogen leaving group to dissipate the resulting energy. Lastly, the HCCH and :CCH2 addition pathways follow through both benzvalene and benzvalyne in order to reach c-C6H6 (benzene) and c-C6H4 (o-benzyne) as well as H2 as the required leaving group. Although there is a barrier to the HCCH addition, the :CCH2 addition presents the contrary with only submerged barriers. These proposed mechanisms provide alternative possibilities for the formation of complex organic molecules in space.

New light on the imbroglio surrounding the C8H+6 isomers formed from ionized azulene and naphthalene using ion-molecule reactions.

Most polycyclic aromatic hydrocarbons (PAHs) can isomerize with internal energies near to or below the dissociation threshold. The C10H+8 group of ions, made up of the naphthalene (Naph+) and the azulene (Azu+) radical cations, is a prototypical example. C8H+6 isomers are important species in the growth kinetics and formation of complex organic molecules, and more generally fragments from larger PAHs, yet information about C8H+6 structures is scarce and contradictory. Here, ion-molecule reactions were carried out and the tunable photoionization chemical monitoring technique was used to probe the C8H+6 isomers formed upon C2H2-loss from Naph+ and Azu+. The experimental findings were interpreted with the support of ab initio and kinetics calculations. To facilitate the interpretation of these data, chemical reactivity starting from phenylacetylene (PA) was studied. It was found that most of the C8H+6 ions formed from C10H8, in a timescale of 40 μs, are PA+ in the vicinity of the dissociation threshold. No evidence of the pentalene radical cation (PE+) was observed and explanations to reconcile previous results are presented.

Determination of the Branching Ratio of CH3OH + OH Reaction on Water Ice Surface at 10 K

The CH3O and CH2OH radicals can be important precursors of complex organic molecules (COMs) in interstellar dust. The COMs presumably originating from these radicals were abundantly found in various astronomical objects. Because each radical leads to different types of COMs, determining the abundance ratio of CH3O to CH2OH is crucial for a better understanding of the chemical evolution into various COMs. Recent work suggested that the reaction between CH3OH and OH on ice dust plays an important role in forming CH3O and CH2OH radicals. However, quantitative details on the abundance of these radicals have not been presented to date. Herein, we experimentally determined the branching ratio (CH3O/CH2OH) resulting from the CH3OH + OH reaction on the water ice surface at 10 K to be 4.3 ± 0.6. Furthermore, the CH3O product in the reaction would participate in subsequent diffusive reactions even at a temperature as low as 10 K. This fact should provide critical information for COMs formation models in cold molecular clouds.

Astrochemically Relevant Radicals and Radical-Molecule Complexes: A New Insight from Matrix Isolation.

The reactive open-shell species play a very important role in the radiation-induced molecular evolution occurring in the cold areas of space and presumably leading to the formation of biologically relevant molecules. This review presents an insight into the mechanism of such processes coming from matrix isolation studies with a main focus on the experimental and theoretical studies performed in the author's laboratory during the past decade. The radicals and radical cations produced from astrochemically relevant molecules were characterized by Fourier transform infrared (FTIR) and electron paramagnetic resonance (EPR) spectroscopy. Small organic radicals containing C, O, and N atoms are considered in view of their possible role in the formation of complex organic molecules (COMs) in space, and a comparison with earlier results is given. In addition, the radical-molecule complexes generated from isolated intermolecular complexes in matrices are discussed in connection with their model significance as the building blocks for COMs formed under the conditions of extremely restricted molecular mobility at cryogenic temperatures.

Observations and Chemical Modeling of the Isotopologues of Formaldehyde and the Cations of Formyl and Protonated Formaldehyde in the Hot Molecular Core G331.512–0.103

In the interstellar cold gas, the chemistry of formaldehyde (H2CO) can be essential to explain the formation of complex organic molecules. On this matter, the massive and energetic protostellar object G331 is still unexplored; hence, we carried out a comprehensive study of the isotopologues of H2CO, the formyl cation (HCO+), and protonated formaldehyde (H2COH+) through the APEX observations in a spectral window of ∼159–356 GHz. We employed observational and theoretical methods to derive the physical properties of the molecular gas combining LTE and non-LTE analyses. Formaldehyde was characterized via 35 lines of H2CO, CO, HDCO, and H2C18O. The formyl cation was detected via eight lines of HCO+, H13CO+, HC18O+, and HC17O+. Deuterium was clearly detected via HDCO, whereas DCO+ remained undetected. The H2COH+ was detected through three clean lines. According to the radiative analysis, formaldehyde appears to be embedded in a bulk gas with a wide range of temperatures (T ∼ 20–90 K), while HCO+ and H2COH+ are primarily associated with colder gas (T ≲ 30 K). The reaction H2CO+HCO+ → H2COH+ + CO is crucial for the balance of the three species. We used the Nautilus gas–grain code to predict the evolution of their molecular abundances relative to H2; their values at timescales of ∼103 yr matched the observations in G331: [H2CO] = (0.2–2) × 10−8, [HCO+] = (0.5–4) × 10−9, and [H2COH+] = (0.2–2) × 10−10. Based on the molecular evolution of H2CO, HCO+, and H2COH+, we hypothesized about the young lifetime of G331, which is consistent with the active gas–grain chemistry of massive protostellar objects.

Formation of Complex Organic Molecules on Interstellar CO Ices? Insights from Computational Chemistry Simulations

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.

Resonant infrared irradiation of CO and CH3OH interstellar ices

Context. Solid-phase photo-processes involving icy dust grains greatly affect the chemical evolution of the interstellar medium by leading to the formation of complex organic molecules and by inducing photodesorption. So far, the focus of laboratory studies has mainly been on the impact of energetic ultraviolet (UV) photons on ices, but direct vibrational excitation by infrared (IR) photons is expected to influence the morphology and content of interstellar ices as well. However, little is still known about the mechanisms through which this excess vibrational energy is dissipated, as well as its implications for the structure and ice photochemistry. Aims. In this work, we present a systematic investigation of the behavior of interstellar relevant CO and CH3OH ice analogs following the resonant excitation of vibrational modes using tunable IR radiation. We seek to quantify the IR-induced photodesorption and gain insights into the impact of vibrational energy dissipation on ice morphology. Methods. We utilized an ultrahigh vacuum setup at cryogenic temperatures to grow pure CO and CH3OH ices, as well as mixtures of the two. We exposed the ices to intense, near-monochromatic mid-IR (MIR) free-electron-laser radiation using the LISA end-station at the FELIX free electron laser facility to selectively excite the species. Changes to the ice are monitored by means of reflection-absorption IR spectroscopy combined with quadrupole mass-spectrometry. These methods also allowed us to characterize the photodesorption efficiency. Results. The dissipation of vibrational energy is observed to be highly dependent on the excited mode and the chemical environment of the ice. All amorphous ices undergo some degree of restructuring towards a more organized configuration upon on-resonance irradiation. Moreover, IR-induced photodesorption is observed to occur for both pure CO and CH3OH ices, with interstellar photodesorption efficiencies on the order of 10 molecules cm−2 s−1. This result is comparable to or higher than what is found for UV-induced counterparts. An indirect photodesorption of CO upon vibrational excitation of CH3OH in ice mixtures is also observed to occur, particularly in environments that are rich in methanol. Here, we discuss the astrochemical implications of these IR-induced phenomena.

Complex Reactive Acids from Methanol and Carbon Dioxide Ice: Glycolic Acid (HOCH2COOH) and Carbonic Acid Monomethyl Ester (CH3OCOOH)

The formation of complex organic molecules by simulated secondary electrons generated in the track of galactic cosmic rays was investigated in interstellar ice analogs composed of methanol and carbon dioxide. The processed ices were subjected to temperature-programmed desorption to mimic the transition of a cold molecular cloud to a warmer star-forming region. Reaction products were detected as they sublime using photoionization reflectron time-of-flight mass spectrometry. By employing isotopic labeling, tunable photoionization and computed adiabatic ionization energies isomers of C2H4O3 were investigated. Product molecules carbonic acid monomethyl ester (CH3OCOOH) and glycolic acid (HOCH2COOH) were identified. The abundance of the reactants detected in analog interstellar ices and the low irradiation dose necessary to form these products indicates that these molecules are exemplary candidates for interstellar detection. Molecules sharing a tautomeric relationship with glycolic acid, dihydroxyacetaldehyde ((OH)2CCHO), and the enol ethenetriol (HOCHC(OH)2), were not found to form despite ices being subjected to conditions that have successfully produced tautomerization in other ice analog systems.

Synthesis of interstellar propen-2-ol (CH3C(OH)CH2) - the simplest enol tautomer of a ketone.

Enols - tautomers of ketones or aldehydes - are anticipated to be ubiquitous in the interstellar medium and play a key role in the formation of complex organic molecules in deep space, but their fundamental formation mechanisms have remained largely elusive as of now. Here we present a combined experimental and computational study demonstrating the first preparation of propen-2-ol (CH3C(OH)CH2) and its isomer methyl vinyl ether (CH3OCHCH2) in low-temperature acetone (CH3COCH3) ices upon exposure to energetic electrons. Propen-2-ol is the simplest enol tautomer of a ketone. Exploiting tunable vacuum ultraviolet photoionization in conjunction with reflectron time-of-flight mass spectrometry, propen-2-ol and methyl vinyl ether were monitored in the gas phase upon sublimation during the temperature-programmed desorption process suggesting that both isomers are promising candidates for future astronomical searches such as via the James Webb Space Telescope. Electronic structure calculations reveal that the barrier of keto-enol tautomerization can be reduced by more than a factor of two (162 kJ mol-1) through the involvement of solvating water molecules under realistic conditions on interstellar grains. The implicit solvent effects, i.e., the influences of the solvent dipole field on the barrier height are found to be minimal and do not exceed 10 kJ mol-1. Our findings signify a crucial step toward a better understanding of the enolization of ketones in the interstellar medium thus constraining the molecular structures and complexity of molecules that form in extraterrestrial ices - ketones - through non-equilibrium chemistry.

Metastable insertion reactions on interstellar ices

ABSTRACT The formation of complex organic molecules (COMs) in interstellar conditions is influenced by several different processes occurring both in the gas and solid phases. Here we perform an extension of previous work to understand the influence of electronically excited metastable species on condensed phase COM formation via insertion-type reactions. These reactions involve the insertion of a chemical entity on a previously existing chemical bond. Such insertion processes involving a metastable species allow for rapid reactions with the surrounding grain ice in the absence of activation energy or diffusion barriers even under cold, dark cloud conditions. In this paper, the production of a number of interstellar species including COMs in cold dark clouds is treated both via the metastable process as well as existing suggested pathways such as radical recombination and hydrogenation of unsaturated species in order to gain insight about the relative importance of the newly added process.

CORINOS. I. JWST/MIRI Spectroscopy and Imaging of a Class 0 Protostar IRAS 15398–3359

The origin of complex organic molecules (COMs) in young Class 0 protostars has been one of the major questions in astrochemistry and star formation. While COMs are thought to form on icy dust grains via gas-grain chemistry, observational constraints on their formation pathways have been limited to gas-phase detection. Sensitive mid-infrared spectroscopy with JWST enables unprecedented investigation of COM formation by measuring their ice absorption features. Mid-infrared emission from disks and outflows provide complementary constraints on the protostellar systems. We present an overview of JWST/Mid-Infrared Instrument (MIRI) Medium Resolution Spectroscopy (MRS) and imaging of a young Class 0 protostar, IRAS 15398−3359, and identify several major solid-state absorption features in the 4.9–28 μm wavelength range. These can be attributed to common ice species, such as H2O, CH3OH, NH3, and CH4, and may have contributions from more complex organic species, such as C2H5OH and CH3CHO. In addition to ice features, the MRS spectra show many weaker emission lines at 6–8 μm, which are due to warm CO gas and water vapor, possibly from a young embedded disk previously unseen. Finally, we detect emission lines from [Fe ii], [Ne ii], [S i], and H2, tracing a bipolar jet and outflow cavities. MIRI imaging serendipitously covers the southwestern (blueshifted) outflow lobe of IRAS 15398−3359, showing four shell-like structures similar to the outflows traced by molecular emission at submillimeter wavelengths. This overview analysis highlights the vast potential of JWST/MIRI observations and previews scientific discoveries in the coming years.

Complex organic molecules formation in cold cores on stochastically heated grains

ABSTRACT We investigate the roles of stochastic grain heating in the formation of complex organic molecules (COMs) in cold cores, where COMs have been detected. Two different types of grain-size distributions are used in the chemical models. The first one is the MRN distribution, and the second one considers grain coagulation to study its effects on the chemical evolution in these environments. The macroscopic Monte Carlo method is used to perform the two-phase chemical model simulations. We find that (1) grain coagulation can affect certain gas-phase species, such as CO2 and N2H+, in the cold core environments, which can be attributed to the volatile precursors originating from the small grains with temperature fluctuations; (2) grains with radii around 4.6 × 10$^{-3}\, \mu$m contribute most to the production of COMs on dust grains under cold core conditions, while few species can be formed on even smaller grains with radii less than 2 × 10$^{-3}\, \mu$m; (3) COMs formed on stochastically heated grains could help explain the observed abundances of gas-phase COMs in cold cores.

On modelling cosmic ray sputtering of interstellar grain ices

ABSTRACT In the interstellar medium (ISM), the formation of complex organic molecules (COMs) is largely facilitated by surface reactions. However, in cold dark clouds, thermal desorption of COMs is inefficient because of the lack of thermal energy to overcome binding energies to the grain surface. Non-thermal desorption methods are therefore important explanations for the gas-phase detection of many COMs that are primarily formed on grains. Here, we present a new non-thermal desorption process: cosmic ray sputtering of grain ice surfaces based on water, carbon dioxide, and a simple mixed ice. Our model applies estimated rates of sputtering to the three-phase rate equation model nautilus-1.1, where this inclusion results in enhanced gas-phase abundances for molecules produced by grain reactions such as methanol (CH3OH) and methyl formate (HCOOCH3). Notably, species with efficient gas-phase destruction pathways exhibit less of an increase in models with sputtering compared to other molecules. These model results suggest that sputtering is an efficient, non-specific method of non-thermal desorption that should be considered as an important factor in future chemical models.