Surface Of Dust Grains Research Articles

Intertwined formation of H2, dust, and stars in cosmological simulations

Context. Molecular hydrogen (H2) plays a crucial role in the formation and evolution of galaxies, serving as the primary fuel reservoir for star formation. In a metal-enriched Universe, H2 forms mostly through catalysis on interstellar dust grain surfaces. However, due to the complexities of modelling this process, star formation in cosmological simulations often relies on empirical or theoretical frameworks that have only been validated in the local Universe to estimate the abundance of H2. Aims. The goal of this work is to model the connection between the processes of star, dust, and H2 formation in our cosmological simulations. Methods. Building upon our recent integration of a dust evolution model into the star formation and feedback model MUPPI, we included the formation of molecular hydrogen on the surfaces of dust grains. We also accounted for the destruction of molecules and their shielding from harmful radiation. Results. The model reproduces, reasonably well, the main statistical properties of the observed galaxy population for the stellar, dust, and H2 components. The evolution of the molecular hydrogen cosmic density (ρH2) in our simulated boxes peaks around redshift z = 1.5, consistent with observations. Following its peak, ρH2 decreases by a factor of two towards z = 0, which is a milder evolution than observed. Similarly, the evolution of the molecular hydrogen mass function since z = 2 displays a gentler evolution when compared to observations. Our model recovers satisfactorily the integrated molecular Kennicut-Schmidt (mKS) law between the surface star formation rate (ΣSFR) and surface H2 density (ΣH2) at z = 0. This relationship is already evident at z = 2, albeit with a higher normalization. We find hints of a broken power law with a steeper slope at higher ΣH2. We also study the H2-to-dust mass ratio in galaxies as a function of their gas metallicity and stellar mass, observing a decreasing trend with respect to both quantities. The H2-to-dust mass fraction for the global population of galaxies is higher at higher redshift. The analysis of the atomic-to-molecular transition on a particle-by-particle basis suggests that gas metallicity cannot reliably substitute the dust-to-gas ratio in models attempting to simulate dust-promoted H2.

Constraining the gas mass of Herbig disks using CO isotopologues

Context. The total disk mass sets the formation potential for exoplanets. Obtaining the disk mass is however not an easy feat, as one needs to consider the optical thickness, temperature, photodissociation, and freeze-out of potential mass tracers. Carbon-monoxide (CO) has been used as a gas mass tracer in T Tauri disks, but was found to be less abundant than expected due to the freeze-out and chemical conversion of CO on the surfaces of cold dust grains. The disks around more massive intermediate mass pre-main sequence stars called Herbig disks are likely to be warmer, allowing for the possibility of using CO as a more effective total gas mass tracer. Aims. This work aims to obtain the gas mass and size of Herbig disks observed with ALMA and compare these to previous works on T Tauri disks and debris disks. Methods. Using ALMA archival data and new NOEMA data of 12CO, 13CO, and C 18O transitions of 35 Herbig disks within 450 pc, the masses were determined using the thermo-chemical code Dust And Lines (DALI). A grid of models was run spanning five orders of magnitude in disk mass, for which the model CO line luminosities could be linked to the observed luminosities. Survival analysis was used to obtain cumulative distributions of the resulting disk masses. These were compared with dust masses from previous work to obtain gas-to-dust ratios for each disk. In addition, radii for all three isotopologues were obtained. Results. The majority of Herbig disks for which 13CO and C18O were detected are optically thick in both. For these disks, the line flux essentially only traces the disk size and only lower limits to the mass can be obtained. Computing the gas mass using a simple optically thin relation between line flux and column density results in an underestimate of the gas mass of at least an order of magnitude compared to the masses obtained with DALI. The inferred gas masses with DALI are consistent with a gas-to-dust ratio of at least 100. These gas-to-dust ratios are two orders of magnitude higher compared to those found for T Tauri disks using similar techniques, even over multiple orders of magnitude in dust mass, illustrating the importance of the chemical conversion of CO in colder T Tauri disks. Similar high gas-to-dust ratios are found for Herbig group I and II disks. Since group II disks have dust masses comparable to T Tauri disks, their higher CO gas masses illustrate the determining role of temperature. Compared to debris disks, Herbig disks have gas masses higher by four orders of magnitude. At least one Herbig disk, HD 163296, has a detected molecular disk wind, but our investigation has not turned up other detections of the CO disk wind in spite of similar sensitivities. Conclusions. Herbig disks are consistent with a gas-to-dust ratio of at least 100 over multiple orders of magnitude in dust mass. This indicates a fundamental difference between CO emission from Herbig disks and T Tauri disks, which is likely linked to the warmer temperature of the Herbig disks.

Modelling deuterated isotopologues of methanol towards the pre-stellar core L1544

Context. In the extremely cold and dark environments of pre-stellar cores, methanol is formed on the surface of interstellar dust grains and released into the gas phase via non-thermal desorption mechanisms. Gaseous methanol constitutes the starting point for the formation of many massive complex organic molecules and is therefore of utmost importance for the build-up of chemical complexity. Aims. We aim to improve upon a previous model for the prediction of column densities and deuterium fractions of non-deuterated and singly deuterated methanol. Thereby, we try to identify crucial chemical and physical parameters for which the study of deuteration could provide valuable additional constraints. Methods. We employed a gas-grain chemical code to devise a model that is in agreement with the observed column density and deuterium fraction profiles of the innermost region of the pre-stellar core L1544. For that purpose, we developed a new treatment of reactive desorption, deriving an individual reactive desorption efficiency for every product species in a chemical reaction that depends on the reaction enthalpy and type of the underlying surface. Furthermore, we explored several options to promote the diffusion of hydrogen and deuterium atoms over the surface of interstellar dust grains in order to increase methanol formation. Results. Our fiducial model employs diffusion via the quantum tunnelling of hydrogen and deuterium atoms, resulting in CH3OH and CH2DOH column densities that are approximately an order of magnitude lower than the observed values, which is an improvement over the results of the previous model by a factor of 10. The N(CH2DOH)/N(CH3OH) ratio is reproduced within a factor of 1.2 for the centre and 1.8 for the position of the methanol peak. Given the large uncertainties that chemical models typically have, we consider our predictions to be in agreement with the observations. In general, we conclude that a diffusion process with a high diffusion rate needs to be employed to obtain methanol column densities that are in accordance with the observed values. Also, we find that the introduction of abstraction reactions into the methanol formation scheme suppresses deuteration when used in combination with a high diffusion rate.

Spectroscopy and Photochemistry of Aluminum-Bearing Species in the Universe.

ConspectusMetal-bearing molecules impact the chemical and physical environment of many astronomical sources such as the circumstellar envelopes of large asymptotic giant branch and red supergiant stars, the interstellar medium, and planetary atmospheres (e.g., ablation of ∼20 tons per day into the Earth's upper atmosphere). In recent decades, the number of successfully detected metal-containing molecules has increased via rotational spectroscopic observations, which are driven by theoretical and experimental investigations. Following formation, the ultimate fate of each species (stabilization, dissociation, etc.) is determined by its electronic structure and electronic spectroscopic properties as it encounters the pervasive radiation fields in the vacuum of space. Studying these properties can evince the possibility of detection and predict the impact each molecule has on its surrounding environment. Aluminum, one of the most abundant elements and metals, is distributed throughout the universe as a constituent of gas-phase molecules (e.g., AlO, AlOH, AlCl, etc.) as well as condensed onto solid dust grains such as Al2O3. Free gas-phase aluminum-bearing molecules are synthesized by nonthermal equilibrium processes such as shocks and pulsations near the stellar photosphere or via the reaction of molecules on the surface of dust grains. Recent investigations in our research group utilizing quantum chemical methods, such as coupled cluster (CCSD(T) and CCSD(T)-F12) and multireference configuration interaction (MRCI) with large basis sets, have explored a wide breadth of spectroscopy and photochemistry of small (triatomic and tetratomic) aluminum-bearing molecules, including Al-H, Al-C, Al-N, Al-O, Al-Si, Al-P, and Al-S bonds, among others. The ground-state spectroscopy (rotational and vibrational) of various aluminum-bearing molecules is discussed in the context of experimental and observational detection potentials. These detection potentials depend on various factors, such as the magnitude of the permanent dipole moment (PDM) and the population of states yielding transition frequencies in detectable ranges. Many aluminum-bearing molecules possess large PDMs and may be prime candidates for astronomical and laboratory detection. Within this discussion, interesting aspects of the ground-state molecular orbital configuration of OAlNO are shown to lead to an uncommon triplet ground state. Additionally, the electronic absorption spectrum of the quasi-isoenergetic ground-state isomers of AlOSO is discussed as a sensitive method for detecting this species and differentiating between the two isomers. Finally, photochemical mechanisms key to the production of AlO and AlOH in low-density regions and the destruction of AlCO and AlOC are also discussed in order to understand the radiation-induced formation and destruction of these molecules.

First Glycine Isomer Detected in the Interstellar Medium: Glycolamide (NH2C(O)CH2OH)

We report the first detection in the interstellar medium (ISM) of a C2H5O2N isomer: syn-glycolamide (NH2C(O)CH2OH). The exquisite sensitivity at sub-mK levels of an ultradeep spectral survey carried out with the Yebes 40 m and IRAM 30 m telescopes toward the G+0.693–0.027 molecular cloud has allowed us to unambiguously identify multiple transitions of this species. We derived a column density of (7.4 ± 0.7) × 1012 cm−2, which implies a molecular abundance with respect to H2 of 5.5 × 10−11. The other C2H5O2N isomers, including the higher-energy anti conformer of glycolamide and two conformers of glycine, were not detected. The upper limit derived for the abundance of glycine indicates that this amino acid is surely less abundant than its isomer glycolamide in the ISM. The abundances of the C2H5O2N isomers cannot be explained in terms of thermodynamic equilibrium; thus, chemical kinetics need to be invoked. While the low abundance of glycine might not be surprising, based on the relative low abundances of acids in the ISM compared to other compounds (e.g., alcohols, aldehydes, or amines), several chemical pathways can favor the formation of its isomer glycolamide. It can be formed through radical–radical reactions on the surface of dust grains. The abundances of these radicals can be significantly boosted in an environment affected by a strong ultraviolet field induced by cosmic rays, such as that expected in G+0.693–0.027. Therefore, as shown by several recent molecular detections toward this molecular cloud, it stands out as the best target to discover new species with carbon, oxygen, and nitrogen with increasing chemical complexity.

Planetary nurseries: vortices formed at smooth viscosity transition

ABSTRACT Excitation of Rossby wave instability and development of a large-scale vortex at the outer dead zone edge of protoplanetary discs is one of the leading theories that explains horseshoe-like brightness distribution in transition discs. Formation of such vortices requires a relatively sharp viscosity transition. Detailed modelling, however, indicates that viscosity transitions at the outer edge of the dead zone is relatively smooth. In this study, we present 2D global, non-isothermal, gas–dust coupled hydrodynamic simulations to investigate the possibility of vortex excitation at smooth viscosity transitions. Our models are based on a recently postulated scenario, wherein the recombination of charged particles on the surface of dust grains results in reduced ionization fraction and, in turn, the turbulence due to magnetorotational instability. Thus, the α-parameter for the disc viscosity depends on the local dust-to-gas mass ratio. We found that the smooth viscosity transitions at the outer edge of the dead zone can become Rossby unstable and form vortices. A single large-scale vortex develops if the dust content of the disc is well coupled to the gas; however, multiple small-scale vortices ensue for the case of less coupled dust. As both type of vortices are trapped at the dead zone outer edge, they provide sufficient time for dust growth. The solid content collected by the vortices can exceed several hundred Earth masses, while the dust-to-gas density ratio within often exceeds unity. Thus, such vortices function as planetary nurseries within the disc, providing ideal sites for formation of planetesimals and eventually planetary systems.

Constraints on the non-thermal desorption of methanol in the cold core LDN 429-C

Context. Cold cores are one of the first steps of star formation, characterized by densities of a few 104–105 cm−3, low temperatures (15 K and below), and very low external UV radiation. In these dense environments, a rich chemistry takes place on the surfaces of dust grains. Understanding the physico-chemical processes at play in these environments is essential to tracing the origin of molecules that are predominantly formed via reactions on dust grain surfaces. Aims. We observed the cold core LDN 429-C (hereafter L429-C) with the NOEMA interferometer and the IRAM 30 m single dish telescope in order to obtain the gas-phase abundances of key species, including CO and CH3OH. Comparing the data for methanol to the methanol ice abundance previously observed with Spitzer allows us to put quantitative constraints on the efficiency of the non-thermal desorption of this species. Methods. With physical parameters determined from available Herschel data, we computed abundance maps of 11 detected molecules with a non-local thermal equilibrium (LTE) radiative transfer model. These observations allowed us to probe the molecular abundances as a function of density (ranging from a few 103 to a few 106 cm−3) and visual extinction (ranging from 7 to over 75), with the variation in temperature being restrained between 12 and 18 K. We then compared the observed abundances to the predictions of the Nautilus astrochemical model. Results. We find that all molecules have lower abundances at high densities and visual extinctions with respect to lower density regions, except for methanol, whose abundance remains around 4.5 × 10−10 with respect to H2. The CO abundance spreads over a factor of 10 (from an abundance of 10−4 with respect to H2 at low density to 1.8 × 10−5 at high density) while the CS, SO, and H2S abundances vary by several orders of magnitude. No conclusion can be drawn for CCS, HC3N, and CN because of the lack of detections at low densities. Comparing these observations with a grid of chemical models based on the local physical conditions, we were able to reproduce these observations, allowing only the parameter time to vary. Higher density regions require shorter times than lower density regions. This result can provide insights on the timescale of the dynamical evolution of this region. The increase in density up to a few 104 cm−3 may have taken approximately 105 yr, while the increase to 106 cm−3 occurs over a much shorter time span (104 yr). Comparing the observed gas-phase abundance of methanol with previous measurements of the methanol ice, we estimate a non-thermal desorption efficiency between 0.002 and 0.09%, increasing with density. The apparent increase in the desorption efficiency cannot be reproduced by our model unless the yield of cosmic-ray sputtering is altered due to the ice composition varying as a function of density.

Investigation of Dust Grains by Optical Tweezers for Space Applications

Cosmic dust plays a dominant role in the universe, especially in the formation of stars and planetary systems. Furthermore, the surface of cosmic dust grains is the benchwork where molecular hydrogen and simple organic compounds are formed. We manipulate individual dust particles in a water solution by contactless and noninvasive techniques such as standard optical and Raman tweezers, to characterize their response to mechanical effects of light (optical forces and torques) and to determine their mineral compositions. Moreover, we show accurate optical force calculations in the T-matrix formalism highlighting the key role of composition and complex morphology in the optical trapping of cosmic dust particles. This opens perspectives for future applications of optical tweezers in curation facilities for sample-return missions or in extraterrestrial environments.

Broadband spectroscopy of astrophysical ice analogues

Context. Broadband optical constants of astrophysical ice analogues in the infrared (IR) and terahertz (THz) ranges are required for modeling the dust continuum emission and radiative transfer in dense and cold regions, where thick icy mantles are formed on the surface of dust grains. Such data are still missing from the literature, which can be attributed to the lack of appropriate spectroscopic systems and methods for laboratory studies. Aims. In this paper, the THz time-domain spectroscopy (TDS) and the Fourier-transform IR spectroscopy (FTIR) are combined to study optical constants of CO and CO2 ices in the broad THz-IR spectral range. Methods. The measured ices were grown at cryogenic temperatures by gas deposition on a cold silicon window. We developed a method to quantify the broadband THz-IR optical constants of ices, based on the direct reconstruction of the complex refractive index of ices in the THz range from the TDS data and the use of the Kramers-Kronig relation in the IR range for the reconstruction from the FTIR data. Uncertainties introduced by the Kramers-Kronig relations were eliminated by merging the THz and IR spectra. Finally, the reconstructed THz-IR response was analyzed using classical models of complex dielectric permittivity. Results. The complex refractive index of CO and CO2 ices deposited at the temperature of 28 K was obtained in the range of 0.312.0 THz and fitted using the analytical Lorentz model. Based on the measured dielectric constants, opacities of the astrophysical dust with CO and CO2 icy mantles were computed. Conclusions. The method developed in this work can be used for a model-independent reconstructions of optical constants of various astrophysical ice analogs in a broad THz-IR range. Such data can provide important benchmarks for interpreting broadband observations from existing and future ground-based facilities and space telescopes. The reported results will be useful in modeling sources that exhibit a drastic molecular freeze-out, such as the central regions of prestellar cores and mid-planes of protoplanetary disks, as well as CO and CO2 snow lines in disks.

Resolving desorption of complex organic molecules in a hot core

Context. The presence of many interstellar complex organic molecules (COMs) in the gas phase in the vicinity of protostars has long been associated with their formation on icy dust grain surfaces before the onset of protostellar activity, and their subsequent thermal co-desorption with water, the main constituent of the grains’ ice mantles, as the protostar heats its environment to ~100 K. Aims. Using the high angular resolution provided by the Atacama Large Millimetre/submillimetre Array (ALMA), we want to resolve the COM emission in the hot molecular core Sagittarius B2 (N1) and thereby shed light on the desorption process of COMs in hot cores. Methods. We used data taken as part of the 3 mm spectral line survey Re-exploring Molecular Complexity with ALMA (ReMoCA) to investigate the morphology of COM emission in Sagittarius B2 (N1). We also used ALMA continuum data at 1 mm taken from the literature. Spectra of ten COMs (including one isotopologue) were modelled under the assumption of local thermodynamic equilibrium (LTE) and population diagrams were derived for these COMs for positions at various distances to the south and west from the continuum peak. Based on this analysis, we produced resolved COM rotation temperature and column density profiles. H2 column density profiles were derived from dust continuum emission and C18O 1–0 emission and used to derive COM abundance profiles as a function of distance and temperature. These profiles are compared to astrochemical models. Results. Based on the morphology, a rough separation into O- and N-bearing COMs can be done. The temperature profiles span a range of 80–300 K with power-law indices from −0.4 to −0.8, which is in agreement with expectations of protostellar heating of an envelope with optically thick dust. Column density and abundance profiles reflect a similar trend as seen in the morphology. While abundances of N-bearing COMs peak only at the highest temperatures, those of most O-bearing COMs peak at lower temperatures and remain constant or decrease towards higher temperatures. Many abundance profiles show a steep increase at ~100 K. To a great extent, the observed results agree with results of astrochemical models that, besides the co-desorption with water, predict that O-bearing COMs are mainly formed on dust-grain surfaces at low temperatures, while at least some N-bearing COMs and CH3CHO are substantially formed in the gas phase at higher temperatures. Conclusions. Our observational results, in comparison with model predictions, suggest that COMs that are exclusively or, to a great extent, formed on dust grains desorb thermally at ~100 K from the grain surface, likely alongside water. A dependence on the COM binding energy is not evident from our observations. Non-zero abundance values below ~100 K suggest that another desorption process of COMs is at work at these low temperatures: either non-thermal desorption or partial thermal desorption related to the lower binding energies experienced by COMs in the outer, water-poor ice layers. In either case, this is the first time that the transition between two regimes of COM desorption has been resolved in a hot core.

The ALMA Survey of 70 μm Dark High-mass Clumps in Early Stages (ASHES). VI. The Core-scale CO Depletion

Studying the physical and chemical properties of cold and dense molecular clouds is crucial for the understanding of how stars form. Under the typical conditions of infrared dark clouds, CO is removed from the gas phase and trapped onto the surface of dust grains by the so-called depletion process. This suggests that the CO-depletion factor (f D ) can be a useful chemical indicator for identifying cold and dense regions (i.e., prestellar cores). We have used the 1.3 mm continuum and C18O (2–1) data observed at the resolution of ∼5000 au in the ALMA Survey of 70 μm Dark High-mass Clumps in Early Stages (ASHES) to construct averaged maps of f D in 12 clumps to characterize the earliest stages of the high-mass star formation process. The average f D determined for 277 of the 294 ASHES cores follows an unexpected increase from the prestellar to the protostellar stage. If we exclude the temperature effect due to the slight variations in the NH3 kinetic temperature among different cores, we explain this result as a dependence primarily on the average gas density, which increases in cores where protostellar conditions prevail. This shows that f D determined in high-mass star-forming regions at the core scale is insufficient to distinguish among prestellar and protostellar conditions for the individual cores and should be complemented by information provided by additional tracers. However, we confirm that the clump-averaged f D values correlate with the luminosity-to-mass ratio of each source, which is known to trace the evolution of the star formation process.

Hydrogen abstraction reactions in formic and thioformic acid isomers by hydrogen and deuterium atoms

Context.The isomerism of molecules in the interstellar medium and the mechanisms behind it are essential questions in the chemistry of organic molecules in space. In the particular case of simple formic and thioformic acids, the low temperatures found in molecular clouds indicate that cis-trans isomerization in the gas-phase must be impeded. Reactions taking place on top of interstellar dust grains may explain the isomer interconversion at low temperatures.Aims.We studied the isomerization processes of formic and thioformic acid that are likely to take place on the surface of interstellar dust grains after being initiated by H abstraction reactions. Similarly, deuterium enrichment of the acids can occur by the same mechanism. Our objective is to shed light on both topics to expand our understanding of the key precursors of organic molecules in space.Methods.We determined the rate constants for the H abstraction reactions as well as the binding energies for the acids on water ice using ab initio calculations and the instanton method for calculating the rate constants, including quantum tunneling. In addition, we tested the viability of the deuteration of formic acid with tailored experiments and looked for it on the L1544 source.Results.For formic acid, there is a clear dependence of the H abstraction reactions on the isomer of the reactant, with rate constants at ~50 K that differ by five orders of magnitude. Correspondingly, we did not observe the trans-cis reaction in our experiments. In the case of thioformic acid, a very similar cis-trans reactivity is found for abstraction reactions at the thiol (-SH) group in contrast to a preferential reactivity that is found when abstractions take place at the -CH moiety. We found comparable binding energies for both isomers with average binding energies of around −6200 and −3100 K for formic and thioformic acid, respectively. Our binding energy calculations show that the reactions are precluded for specific orientations, affecting the overall isomerization rate. For H abstractions initiated by deuterium atoms, we found very similar trends, with kinetic isotope effects varying in most cases between 13 and 20.Conclusions.Our results support the cis-trans interconversion of cis-formic acid on dust grains, suggesting that such an acid should not withstand the conditions found on these objects. On the other hand, the trans isomer is very resilient. Both isomers of thioformic acid are much more reactive. A non-trivial chemistry is behind the apparent excess of its trans isomer that is found in cold molecular clouds and star-forming regions due to a subtle combination of preferential reactivity and binding with the surface. In light of our results, all the deuterated counterparts of thioformic acid are viable molecules to be present on the ISM. In contrast, only the trans isomer of deuterated formic acid is expected, for which we provide upper bounds of detection. Given the mechanisms presented in this paper, other mechanisms must be at play to explain the tiny fraction of cis-formic acid observed in interstellar cold environments, as well as the current trans-DCOOH and trans-HCOOD abundances in hot-corinos.

We Drink Good 4.5-Billion-Year-Old Water

Water is crucial for the emergence and evolution of life on Earth. Recent studies of the water content in early forming planetary systems similar to our own show that water is an abundant and ubiquitous molecule, initially synthesized on the surfaces of tiny interstellar dust grains by the hydrogenation of frozen oxygen. Water then enters a cycle of sublimation/freezing throughout the successive phases of planetary system formation, namely, hot corinos and protoplanetary disks, eventually to be incorporated into planets, asteroids, and comets. The amount of heavy water measured on Earth and in early forming planetary systems suggests that a substantial fraction of terrestrial water was inherited from the very first phases of the Solar System formation and is 4.5 billion years old.

The Prospects for Hurricane-like Vortices in Protoplanetary Disks

When ice on the surface of dust grains in protoplanetary disk sublimates, it adds its latent heat of water sublimation to the surrounding flow. Drawing on the analogy provided by tropical cyclones on Earth, we investigate whether this energy source is sufficient to sustain or magnify anticyclonic disk vortices that would otherwise fall victim to viscous dissipation. An analytical treatment, supported by exploratory two-dimensional simulations, suggests that even modestly undersaturated flows can extend the lifetime of vortices, potentially to a degree sufficient to aid particle trapping and planetesimal formation. We expect the best conditions for this mechanism to occur will be found near the disk’s water ice line if turbulent motions displace gas parcels out of thermodynamic equilibrium with the dust midplane.

AlOSO: Spectroscopy and Structure of a New Group of Astrochemical Molecules

With the ever-increasing detection of sulfur-bearing molecules and the high abundance and refractory nature of aluminum, the [Al, S, O2] isomers may play an important role in the gas-phase chemistry of circumstellar envelopes and the chemistry on the surface of dust grains. High-level theoretical exploration of the [Al, S, O2] molecular system yielded five isomers, and predictions of their rotational, vibrational, and electronic spectroscopic properties are provided to inform experimental and observational searches. Cis-AlOSO and diamond isomers are isoenergetic and connected via a very small (∼1 kcal mol−1) transition-state barrier. These isomers may act as intermediates along the chemical pathway between Al + SO2 and AlO + SO. Other isomers OAlOS and SAlO2 are stable relative to their corresponding dissociation asymptotes. Large permanent dipole moments of 2.521 D (cis-AlOSO), 1.239 D (diamond), and 5.401 D (OAlOS) predict strong rotational transitions and indicate these molecules as prime candidates for experimental study. Due to the low transition-state barrier, mixing of the vibrational levels is anticipated, complicating the vibrational spectrum. Electronic spectroscopy may be used as a means to differentiate between the two isomers. Strong electronic transitions are predicted to occur in the 200–300 nm range for cis-AlOSO and diamond. Simulated electronic absorption spectra provide a starting point for experimental characterization and spectral deconvolution of these isomers.

The Central 1000 au of a Prestellar Core Revealed with ALMA. II. Almost Complete Freeze-out

Abstract Prestellar cores represent the initial conditions in the process of star and planet formation. Their low temperatures (<10 K) allow the formation of thick icy dust mantles, which will be partially preserved in future protoplanetary disks, ultimately affecting the chemical composition of planetary systems. Previous observations have shown that carbon- and oxygen-bearing species, in particular CO, are heavily depleted in prestellar cores due to the efficient molecular freeze-out onto the surface of cold dust grains. However, N-bearing species such as NH3 and, in particular, its deuterated isotopologues appear to maintain high abundances where CO molecules are mainly in the solid phase. Thanks to ALMA, we present here the first clear observational evidence of NH2D freeze-out toward the L1544 prestellar core, suggestive of the presence of a “complete depletion zone” within a ≃1800 au radius, in agreement with astrochemical prestellar core model predictions. Our state-of-the-art chemical model coupled with a non-LTE radiative transfer code demonstrates that NH2D becomes mainly incorporated in icy mantles in the central 2000 au and starts freezing out already at ≃7000 au. Radiative transfer effects within the prestellar core cause the NH2D(111 − 101) emission to appear centrally concentrated, with a flattened distribution within the central ≃3000 au, unlike the 1.3 mm dust continuum emission, which shows a clear peak within the central ≃1800 au. This prevented NH2D freeze-out from being detected in previous observations, where the central 1000 au cannot be spatially resolved.

Formation of Complex Organic Molecules in Hot Molecular Cores through Nondiffusive Grain-surface and Ice-mantle Chemistry

Abstract A new, more comprehensive model of gas–grain chemistry in hot molecular cores is presented, in which nondiffusive reaction processes on dust-grain surfaces and in ice mantles are implemented alongside traditional diffusive surface/bulk-ice chemistry. We build on our nondiffusive treatments used for chemistry in cold sources, adopting a standard collapse/warm-up physical model for hot cores. A number of other new chemical model inputs and treatments are also explored in depth, culminating in a final model that demonstrates excellent agreement with gas-phase observational abundances for many molecules, including some (e.g., methoxymethanol) that could not be reproduced by conventional diffusive mechanisms. The observed ratios of structural isomers methyl formate, glycolaldehyde, and acetic acid are well reproduced by the models. The main temperature regimes in which various complex organic molecules (COMs) are formed are identified. Nondiffusive chemistry advances the production of many COMs to much earlier times and lower temperatures than in previous model implementations. Those species may form either as by-products of simple-ice production, or via early photochemistry within the ices while external UV photons can still penetrate. Cosmic ray-induced photochemistry is less important than in past models, although it affects some species strongly over long timescales. Another production regime occurs during the high-temperature desorption of solid water, whereby radicals trapped in the ice are released onto the grain/ice surface, where they rapidly react. Several recently proposed gas-phase COM-production mechanisms are also introduced, but they rarely dominate. New surface/ice reactions involving CH and CH2 are found to contribute substantially to the formation of certain COMs.

Sulfur gas-phase abundance in dense cores

The abundance of volatile sulfur in dense clouds is long-standing problem in studies of the physics and chemistry of star-forming regions. Sulfur is an important species because its low ionization potential may possibly make it an important charge carrier. The observed sulfur-bearing species in the gas-phase of dense clouds represent only a minor fraction of the cosmic sulfur abundance, which has been interpreted as a signature of sulfur depletion into ices at the surface of dust grains. However, atomic sulfur, which could be the main gas-phase carrier, cannot be observed directly in cold cores. We present measurements of the nitrogen sulfide (NS) radical toward four dense cores performed with the IRAM-30m telescope. Analytical chemical considerations and chemical models over a wide parameter space show that the NS:N2H+ abundance ratio provides a direct constraint on the abundance of gas-phase atomic sulfur. Toward early-type cores, we find that n(S)∕nH is close, or even equal, to the cosmic abundance of sulfur, 14 × 10−6, demonstrating that sulfur is not depleted and is atomic, which is in agreement with chemical models. More chemically evolved cores show sulfur depletion by factors up to 100 in their densest parts. In L1544, atomic sulfur depletion is shown to increase with increasing density. Future observations are needed to discover the solid-phase carrier of sulfur. The initial steps of the collapse of pre-stellar cores in the high sulfur abundance regime also need to be explored from their chemical and dynamical perspectives.

Understanding the impact of diffusion of CO in the astrochemical models

Abstract The mobility of lighter species on the surface of interstellar dust grains plays a crucial role in forming simple through complex molecules. Carbon monoxide is one of the most abundant molecules, its surface diffusion on the grain surface is essential to forming many molecules. Recent laboratory experiments found a diverse range of diffusion barriers for CO on the grain surface, their use can significantly impact the abundance of several molecules. The impact of different diffusion barriers of CO, in the astrochemical models, is studied to understand its effect on the abundance of solid CO and the species for which it is a reactant partner. A gas-grain network is used for three different physical conditions; cold core and warm-up models with slow and fast heating rates. Two different ratios (0.3 and 0.5) between diffusion and desorption barrier are utilised for all the species. For each physical condition and ratio, six different models are run by varying diffusion barriers of CO. Solid CO abundance for the models with the lowest diffusion barrier yields less than 0.1% of water ice for cold clouds and a maximum of 0.4% for slow and fast warm-up models. Also, solid $\textrm{CO}_2$ in dense clouds is significantly overproduced ( ${\sim}140\%$ of water). The abundance of H2CO and $\textrm{CH}_3\textrm{OH}$ showed an opposite trend, and HCOOH, $\textrm{CH}_3\textrm{CHO}$ , $\textrm{NH}_2\textrm{CO}$ , and $\textrm{CH}_3\textrm{COCH}_3$ are produced in lower quantities for models with low diffusion barriers for CO. Considerable variation in abundance is observed between models with the high and low diffusion barrier. Models with higher diffusion barriers provide a relatively better agreement with the observed abundances when compared with the models having lower diffusion barriers.

Unusual Chemical Processes in Interstellar Chemistry: Past and Present

The chemistry that occurs in interstellar clouds consists of both gas-phase processes and reactions on the surfaces of dust grains, the latter particularly on and in water-dominated ice mantles in cold clouds. Some of these processes, especially at low temperature, are very unusual by terrestrial standards. For example, in the gas-phase, two-body association reactions form a metastable species known as a complex, which is then stabilized by the emission of radiation under low-density conditions, especially at low temperatures. In the solid phase, it has been thought that the major process for surface reactions is diffusive in nature, occurring when two species undergoing random walks collide with each other on a surface that has both potential wells and intermediate barriers. There is experimental evidence for this process, although very few rates at low interstellar temperatures are well measured. Moreover, since dust particles are discrete, modeling has to take account that reactant pairs are on the same grain, a problem that can be treated using stochastic approaches. In addition, it has been shown more recently that surface reactions can occur more rapidly if they undergo any of a number of non-diffusive processes including so-called three-body mechanisms. There is some experimental support for this hypothesis. These and other unusual gaseous and solid-state processes will be discussed from the theoretical and experimental points of view, and their possible role in the synthesis of organic molecules in interstellar clouds explained. In addition, their historical development will be reviewed.