Gas-grain Chemical Model Research Articles

Carbon Isotope Fractionation of Complex Organic Molecules in Star-forming Cores

Recent high-resolution and sensitivity Atacama Large Millimeter/submillimeter Array observations have unveiled the carbon isotope ratios (12C/13C) of complex organic molecules (COMs) in a low-mass protostellar source. To understand the 12C/13C ratios of COMs, we investigated the carbon isotope fractionation of COMs from prestellar cores to protostellar cores with a gas-grain chemical network model. We confirmed that the 12C/13C ratios of small molecules are bimodal in the prestellar phase: CO and species formed from CO (e.g., CH3OH) are slightly enriched in 13C compared to the local interstellar medium (by ∼10%), while those from C and C+ are depleted in 13C owing to isotope exchange reactions. COMs are mainly formed on the grain surface and in the hot gas (> 100 K) in the protostellar phase. The 12C/13C ratios of COMs depend on which molecules the COMs are formed from. In our base model, some COMs in the hot gas are depleted in 13C compared to the observations. Thus, we additionally incorporate reactions between gaseous atomic C and H2O ice or CO ice on the grain surface to form H2CO ice or C2O ice, as suggested by recent laboratory studies. The direct C-atom addition reactions open pathways to form 13C-enriched COMs from atomic C and CO ice. We find that these direct C-atom addition reactions mitigate 13C-depletion of COMs, and the model with the direct C-atom addition reactions better reproduces the observations than our base model. We also discuss the impact of the cosmic-ray ionization rate on the 12C/13C ratio of COMs.

Quasi-equilibrium chemical evolution in starless cores

ABSTRACT The chemistry of H2O, CO, and other small molecular species in an isolated pre-stellar core, L1544, has been assessed in the context of a comprehensive gas-grain chemical model, coupled to an empirically constrained physical/dynamical model. Our main findings are (i) that the chemical network remains in near equilibrium as the core evolves towards star formation and the molecular abundances change in response to the evolving physical conditions. The gas-phase abundances at any time can be calculated accurately with equilibrium chemistry, and the concept of chemical clocks is meaningless in molecular clouds with similar conditions and dynamical time-scales, and (ii) A comparison of the results of complex and simple chemical networks indicates that the abundances of the dominant oxygen and carbon species, H2O, CO, C, and C+ are reasonably approximated by simple networks. In chemical equilibrium, the time-dependent differential terms vanish, and a simple network reduces to a few algebraic equations. This allows rapid calculation of the abundances most responsible for spectral line radiative cooling in molecular clouds with long dynamical time-scales. The dust ice mantles are highly structured and the ice layers retain a memory of the gas-phase abundances at the time of their deposition. A complex (gas-phase and gas-grain) chemical structure therefore exists, with cosmic-ray induced processes dominating in the inner regions. The inferred H2O abundance profiles for L1544 require that the outer parts of the core and also any medium exterior to the core are essentially transparent to the interstellar radiation field.

Combined model for 15N, 13C, and spin-state chemistry in molecular clouds

We present a new gas-grain chemical model for the combined isotopic fractionation of carbon and nitrogen in molecular clouds. To this end, we have developed gas-phase and grain-surface chemical networks where the isotope chemistry of carbon and nitrogen is coupled with a time-dependent description of spin-state chemistry, which is important for nitrogen chemistry at low temperatures. We updated the rate coefficients of some isotopic exchange reactions considered previously in the literature, and here we present a set of new exchange reactions involving molecules substituted in 13C and 15N simultaneously. We applied the model to a series of zero-dimensional simulations representing a set of physical conditions across a prototypical prestellar core, exploring the deviations of the isotopic abundance ratios in the various molecules from the elemental isotopic ratios as a function of physical conditions and time. We find that the 12C/13C ratio can deviate from the elemental ratio to a high factor depending on the molecule, and that there are highly time-dependent variations in the ratios. The HCN/H13CN ratio, for example, can obtain values of less than ten depending on the simulation time. The 14N/15N ratios tend to remain close to the assumed elemental ratio within approximately 10%, with no clearly discernible trends for the various species as a function of the physical conditions. Abundance ratios between 13C-containing molecules and 13C+15N-containing molecules however show somewhat increased levels of fractionation as a result of the newly included exchange reactions, though they still remain within a few tens of percent of the elemental 14N/15N ratio. Our results imply the existence of gradients in isotopic abundance ratios across prestellar cores, suggesting that detailed simulations are required to interpret observations of isotopically substituted molecules correctly, especially given that the various isotopic forms of a given molecule do not necessarily trace the same gas layers.

3D physico-chemical model of a pre-stellar core

Context. Pre-stellar cores represent the earliest stage of the formation process of stars and planets. By characterizing the physical and chemical structure of these cores, we can establish the initial conditions for star and planet formation and determine to what degree the chemical composition of pre-stellar cores is inherited by the later stages. Aims. We aim to determine the underlying causes of spatial chemical segregation observed in pre-stellar cores and study the effects of the core structure and external environment on the chemical structure of pre-stellar cores. Methods. A three-dimensional (3D) magnetohydrodynamic model of a pre-stellar core embedded in a dynamic star-forming cloud was post-processed with a sequentially continuum radiative transfer, a gas-grain chemical model, and a line-radiative transfer model. The results were analyzed and compared to observations of CH3OH and c-C3H2 in L1544. We compared nine different chemical models to the observations to determine which initial conditions are compatible with the observed chemical segregation in the prototypical pre-stellar core L1544. Results. The model is able to reproduce several aspects of the observed chemical differentiation in L1544. Extended methanol emission is shifted towards colder and more shielded regions of the core envelope, while c-C3H2 emission overlaps with the dust continuum, which is consistent with the observed chemical structure. Furthermore, these results are consistent across a broad spectrum of chemical models. Increasing the strength of the interstellar radiation field or the cosmic-ray ionization rate with respect to the typical values assumed in nearby star-forming regions leads to synthetic maps that are inconsistent with the observed chemical structure. Conclusions. Our model shows that the observed chemical dichotomy in L1544 can arise as a result of uneven illumination due to the asymmetrical structure of the 3D core and the environment within which the core has formed. This highlights the importance of the 3D structure at the core-cloud transition on the chemistry of pre-stellar cores. The reported effect is likely to affect later stages of the formation process of stars and planets through chemical inheritance.

Oscillations in gas-grain astrochemical kinetics

ABSTRACT We have studied gas-grain chemical models of interstellar clouds to search for non-linear dynamical evolution. A prescription is given for producing oscillatory solutions when a bistable solution exists in the gas-phase chemistry and we demonstrate the existence of limit cycle and relaxation oscillation solutions. As the autocatalytic chemical processes underlying these solutions are common to all models of interstellar chemistry, the occurrence of these solutions should be widespread. We briefly discuss the implications for interpreting molecular cloud composition with time-dependent models and some future directions for this approach.

Impact of HAC evolution on the formation of small hydrocarbons in the Orion Bar and the Horsehead PDRs

ABSTRACT We study evolution of hydrogenated amorphous carbon (HAC) grains under harsh UV radiation in photodissociation regions (PDRs) near young massive stars. Our aim is to evaluate the impact of the HAC grains on formation of observed small hydrocarbons: C2H, C2H2, C3H+, C3H, C3H2, C4H, in PDRs. We developed a microscopic model of the HAC grains based on available experimental results. The model includes processes of photo and thermo-desorption, accretion of hydrogen and carbon atoms and subsequent formation of carbonaceous mantle on dust surface. H2, CH4, C2H2, C2H4, C2H6, C3H4, C3H6, C3H8 are considered as the main fragments of the HAC photodestruction. We simulated evolution of the HAC grains under the physical conditions of two PDRs, the Orion Bar and the Horsehead nebula. We estimated the production rates of the HAC’ fragments in gas phase chemical reactions and compared them with the production rates of fragments due to the HAC destruction. The latter rates may dominate under some conditions, namely, at AV = 0.1 in both PDRs. We coupled our model with the gas-grain chemical model MONACO and calculated abundances of observed small hydrocarbons. We conclude that the contribution of the HAC destruction fragments to chemistry is not enough to match the observed abundances, although it increases the abundances by several orders of magnitude in the Orion Bar at AV = 0.1. Additionally, we found that the process of carbonaceous mantle formation on dust surface can be an inhibitor for the formation of observed small hydrocarbons in PDRs.

Laboratory spectroscopy of theoretical ices: Predictions for JWST and test for astrochemical models

Context. The pre-stellar core L1544 has been the subject of several observations conducted in the past years, complemented by modelling studies focused on its gas and ice-grain chemistry. The chemical composition of the ice mantles reflects the environmental physical changes along the temporal evolution, such as density and temperature. The investigation outcome hints at a layered structure of interstellar ices with abundance of H2O in the inner layers and an increasing concentration of CO near the surface. The morphology of interstellar ice analogues can be investigated experimentally assuming a composition derived from chemical models. Aims. This research presents a new approach of a three-dimensional fit where observational results are first fitted with a gas-grain chemical model predicting the exact ice composition including infrared (IR) inactive species. Then the laboratory IR spectra are recorded for interstellar ice analogues whose compositions reflect the obtained numerical results, in a layered and in a mixed morphology. These results could then be compared with the results of James Webb Space Telescope (JWST) observations. Special attention is paid to the inclusion of IR inactive species whose presence is predicted in the ice, but is typically omitted in the laboratory obtained data. This stands for N2, one of the main possible constituents of interstellar ice mantles, and O2. Methods. Ice analogue spectra were recorded at a temperature of 10 K using a Fourier transform infrared spectrometer. In the case of layered ice we deposited a H2O-CO-N2-O2 mixture on top of a H2O-CH3OH-N2 ice, while in the case of mixed ice we examined a H2O-CH3OH-N2-CO composition. The selected species are the four most abundant ice components predicted by the chemical model. Results. Following the changing composition and structure of the ice, we find differences in the absorption bands for most of the examined vibrational modes. The extent of observed changes in the IR band profiles will allow us to analyse the structure of ice mantles in L1544 from future observations by the JWST. Conclusions. Our spectroscopic measurements of interstellar ice analogues predicted by our well-received gas-grain chemical codes of pre-stellar cores will allow detailed comparison with upcoming JWST observations. This is crucial in order to put stringent constraints on the chemical and physical structure of dust icy mantles just before the formation of stars and protoplanetary disks, and to explain surface chemistry.

A survey of HDCO and D2CO towards Class 0/I proto-brown dwarfs

ABSTRACT Deuterium fractionation can constrain the physical and chemical conditions at the early stage of brown dwarf formation. We present IRAM 30-m observations over a wide frequency range of 213–279 GHz of singly and doubly deuterated species of formaldehyde (HDCO and D2CO) towards Class 0/I proto-brown dwarfs (proto-BDs). Multiple low-excitation HDCO and D2CO transition lines with upper energy level ≤40 K are detected. The D2CO/HDCO, HDCO/H2CO, and D2CO/H2CO abundance ratios range between 0.01 and 2.5 for the proto-BDs, similar to the range seen in low-mass protostars. The highest ratios of D2CO/HDCO ∼1.3–2.5 are measured for two Stage 0 proto-BDs. These objects could possess a warm corino, similar to the few hot corino cases reported among Class 0 protostars. The mean D2CO/HDCO, D2CO/H2CO, and HDCO/H2CO ratios for the proto-BDs are comparatively higher than the range predicted by the current gas-grain chemical models, indicating that HDCO and D2CO are formed via grain surface reactions in the dense and cold interiors of the proto-BDs at an early formation stage.

The cosmic-ray ionisation rate in the pre-stellar core L1544

Context. Cosmic rays (CRs), which are energetic particles mainly composed of protons and electrons, play an important role in the chemistry and dynamics of the interstellar medium. In dense environments, they represent the main ionising agent, hence driving the rich chemistry of molecular ions. Furthermore, they determine the ionisation fraction, which regulates the degree of coupling between the gas and the interstellar magnetic fields, and the heating of the gas. Estimates of the CR ionisation rate of molecular hydrogen (ζ2) span several orders of magnitude, depending on the targeted sources and on the method used. Aims. Recent theoretical models have characterised the CR attenuation with increasing density. We aim to test these models for the attenuation of CRs in the low-mass pre-stellar core L1544. Methods. We used a state-of-the-art gas-grain chemical model, which accepts the CR ionisation rate profile as input, to predict the abundance profiles of four ions: N2H+, N2D+, HC18O+, and DCO+. Non-local thermodynamic equilibrium radiative transfer simulations were run to produce synthetic spectra based on the derived abundances. These were compared with observations obtained with the Institut de Radioastronomie Millimétrique 30 m telescope. Results. Our results indicate that a model with high ζ2 (>10−16 s−1) is excluded by the observations. Also the model with the standard ζ2 = 1.3 × 10−17 s−1 produces a worse agreement with respect to the attenuation model based on Voyager observations, which is characterised by an average ⟨ ζ2 ⟩ = 3 × 10−17 s−1 at the column densities typical of L1544. The single-dish data, however, are not sensitive to the attenuation of the CR profile, which changes only by a factor of two in the range of column densities spanned by the core model (N = 2−50 × 1021 cm−2). Interferometric observations at higher spatial resolution, combined with observations of transitions with lower critical density – hence tracing the low-density envelope – are needed to observe a decrease in the CR ionisation rate with density.

HCN/HNC chemistry in shocks: a study of L1157-B1 with ASAI

ABSTRACT Hydrogen cyanide (HCN) and its isomer hydrogen isocyanide (HNC) play an important role in molecular cloud chemistry and the formation of more complex molecules. We investigate here the impact of protostellar shocks on the HCN and HNC abundances from high-sensitivity IRAM 30 m observations of the prototypical shock region L1157-B1 and the envelope of the associated Class 0 protostar, as a proxy for the pre-shock gas. The isotopologues H12CN, HN12C, H13CN, HN13C, HC15N, H15NC, DCN, and DNC were all detected towards both regions. Abundances and excitation conditions were obtained from radiative transfer analysis of molecular line emission under the assumption of local thermodynamical equilibrium. In the pre-shock gas, the abundances of the HCN and HNC isotopologues are similar to those encountered in dark clouds, with an HCN/HNC abundance ratio ≈1 for all isotopologues. A strong D-enrichment (D/H ≈ 0.06) is measured in the pre-shock gas. There is no evidence of 15N fractionation neither in the quiescent nor in the shocked gas. At the passage of the shock, the HCN and HNC abundances increase in the gas phase in different manners so that the HCN/HNC relative abundance ratio increases by a factor 20. The gas-grain chemical and shock model uclchem allows us to reproduce the observed trends for a C-type shock with pre-shock density n(H) = $10^5\hbox{cm$^{-3}$}$ and shock velocity $V_\mathrm{ s}= 40\hbox{kms$^{-1}$}$. We conclude that the HCN/HNC variations across the shock are mainly caused by the sputtering of the grain mantle material in relation with the history of the grain ices.

Combined hydrodynamic and gas-grain chemical modeling of hot cores

Context. Gas-grain models have long been employed to simulate hot-core chemistry; however, these simulations have traditionally neglected to couple chemical evolution in tandem with a rigorous physical evolution of a source. This over-simplification particularly lacks an accurate treatment of temperature and spatial distribution, which are needed for realistic simulations of hot cores. Aims. We aim to combine radiation hydrodynamics (RHD) with hot-core chemical kinetics in one dimension to produce a set of astrochemical models that evolve according to explicitly calculated temperature, density, and spatial profiles. Methods. We solve radiation hydrodynamics for three mass-accretion-rate models using Athena++. We then simulate the chemistry using the hot-core chemical kinetic code MAGICKAL according to the physics derived from the RHD treatment. Results. We find that as the mass-accretion rate decreases, the overall gas density of the source decreases. In particular, the gas density for the lowest mass-accretion rate is low enough to restrict the proper formation of many complex organic molecules. We also compare our chemical results in the form of calculated column densities to those of observations toward Sgr B2(N2). We find a generally good agreement for oxygen-bearing species, particularly for the two highest mass-accretion rates. Conclusions. Although we introduce hot-core chemical modeling using a self-consistent physical treatment, the adoption of a two-dimensional model may better reproduce chemistry and physics toward real sources and thus achieve better chemical comparisons with observations.

Chemical modeling of the complex organic molecules in the extended region around Sagittarius B2

Context. The chemical differentiation of seven complex organic molecules (COMs) in the extended region around Sagittarius B2 (Sgr B2) has been previously observed: CH2OHCHO, CH3OCHO, t-HCOOH, C2H5OH, and CH3NH2 were detected both in the extended region and near the hot cores Sgr B2(N) and Sgr B2(M), while CH3OCH3 and C2H5CN were only detected near the hot cores. The density and temperature in the extended region are relatively low in comparison with Sgr B2(N) and Sgr B2(M). Different desorption mechanisms, including photodesorption, reactive desorption, and shock heating, and a few other mechanisms have been proposed to explain the observed COMs in the cold regions. However, they fail to explain the deficiency of CH3OCH3 and C2H5CN in the extended region around Sgr B2. Aims. Based on known physical properties of the extended region around Sgr B2, we explored under what physical conditions the chemical simulations can fit the observations and explain the different spatial distribution of these seven species in the extended region around Sgr B2. Methods. We used the macroscopic Monte Carlo method to perform a detailed parameter space study. A static physical model and an evolving physical model including a cold phase and a warm-up phase were used, respectively. The fiducial models adopt the observed physical parameters except for the local cosmic ray ionization rate ζCR. In addition to photodesorption that is included in all models, we investigated how chain reaction mechanism, shocks, an X-ray burst, enhanced reactive desorption and low diffusion barriers could affect the results of chemical modeling. Results. All gas-grain chemical models based on static physics cannot fit the observations, except for the high abundances of CH3NH2 and C2H5CN in some cases. The simulations based on evolving physical conditions can fit six COMs when T ~ 30−60 K in the warm-up phase, but the best-fit temperature is still higher than the observed dust temperature of 20 K. The best agreement between the simulations and all seven observed COMs at a lower temperature T ~ 27 K is achieved by considering a short-duration ≈102 yr X-ray burst with ζCR = 1.3 × 10−13 s−1 at the early stage of the warm-up phase when it still has a temperature of 20 K. The reactive desorption is the key mechanism for producing these COMs and inducing the low abundances of CH3OCH3 and C2H5CN. Conclusions. We conclude that the evolution of the extended region around Sgr B2 may have begun with a cold, T ≤ 10 K phase followed by a warm-up phase. When its temperature reached about T ~ 20 K, an X-ray flare from the Galactic black hole Sgr A* with a short duration of no more than 100 yr was acquired, affecting strongly the Sgr B2 chemistry. The observed COMs in Sgr B2 are able to retain their observed abundances only several hundred years after such a flare, which could imply that such short-term X-rays flares occur relatively often, likely associated with the accretion activity of the Sgr A* source.

Gas-grain model of carbon fractionation in dense molecular clouds

ABSTRACT Carbon containing molecules in cold molecular clouds show various levels of isotopic fractionation through multiple observations. To understand such effects, we have developed a new gas-grain chemical model with updated 13C fractionation reactions (also including the corresponding reactions for 15 N, 18O, and 34S). For chemical ages typical of dense clouds, our nominal model leads to two 13C reservoirs: CO and the species that derive from CO, mainly s-CO and s-CH3OH, as well as C3 in the gas phase. The nominal model leads to strong enrichment in C3, c-C3H2, and C2H in contradiction with observations. When C3 reacts with oxygen atoms, the global agreement between the various observations and the simulations is rather good showing variable 13C fractionation levels that are specific to each species. Alternatively, hydrogen atom reactions lead to notable relative 13C fractionation effects for the two non-equivalent isotopologues of C2H, c-C3H2, and C2S. As there are several important fractionation reactions, some carbon bearing species are enriched in 13C, particularly CO, depleting atomic 13C in the gas phase. This induces a 13C depletion in CH4 formed on grain surfaces, an effect that is not observed in the CH4 in the Solar system, in particular on Titan. This seems to indicate a transformation of matter between the collapse of the molecular clouds, leading to the formation of the protostellar disc, and the formation of the planets. Or it means that the atomic carbon sticking to the grains reacts with the species already on the grains giving very little CH4.

First detection of NHD and ND2 in the interstellar medium

Context. Deuterium fractionation processes in the interstellar medium (ISM) have been shown to be highly efficient in the family of nitrogen hydrides. To date, observations have been limited to ammonia (NH2D, NHD2, ND3) and imidogen radical (ND) isotopologues. Aims. We want to explore the high-frequency windows offered by the Herschel Space Observatory to search for deuterated forms of the amidogen radical NH2 and to compare the observations against the predictions of our comprehensive gas-grain chemical model. Methods. Making use of the new molecular spectroscopy data recently obtained at high frequencies for NHD and ND2, we searched for both isotopologues in the spectral survey toward the Class 0 protostar IRAS 16293-2422, a source in which NH3, NH, and their deuterated variants have previously been detected. We used the observations carried out with HIFI (Heterodyne Instrument for the Far-Infrared) in the framework of the key program “Chemical Herschel surveys of star forming regions” (CHESS). Results. We report the first detection of interstellar NHD and ND2. Both species are observed in absorption against the continuum of the protostar. From the analysis of their hyperfine structure, accurate excitation temperature and column density values are determined. The latter were combined with the column density of the parent species NH2 to derive the deuterium fractionation in amidogen. We find a high deuteration level of amidogen radical in IRAS 16293-2422, with a deuterium enhancement about one order of magnitude higher than that predicted by earlier astrochemical models. Such a high enhancement can only be reproduced by a gas-grain chemical model if the pre-stellar phase preceding the formation of the protostellar system has a long duration: on the order of one million years. Conclusions. The amidogen D/H ratio measured in the low-mass protostar IRAS 16293-2422 is comparable to that derived for the related species imidogen and much higher than that observed for ammonia. Additional observations of these species will provide more insights into the mechanism of ammonia formation and deuteration in the ISM. Finally, we indicate the current possibilities to further explore these species at submillimeter wavelengths.

Effect of grain size distribution and size-dependent grain heating on molecular abundances in starless and pre-stellar cores

We present a new gas-grain chemical model to constrain the effect of grain size distribution on molecular abundances in physical conditions corresponding to starless and pre-stellar cores. We simultaneously introduce grain-size dependence for desorption efficiency induced by cosmic rays (CRs) and for grain equilibrium temperatures. The latter were calculated with a radiative transfer code via custom dust models built for the present work. We explicitly tracked of ice abundances on a set of grain populations. We find that the size-dependent CR desorption efficiency affects ice abundances in a highly nontrivial way that depends on the molecule. Species that originate in the gas phase, such as CO, follow a simple pattern in which the ice abundance is highest on the smallest grains and these are the most abundant in the distribution. Some molecules, such as HCN, are instead concentrated on large grains throughout the time evolution; others, such as N2, are initially concentrated on large grains, but at late times on small grains because of grain-size-dependent competition between desorption and hydrogenation. Most of the water ice is on small grains at high medium density (n(H2) ≳ 106 cm−3), where the water ice fraction, with respect to the total water ice reservoir, can be as low as ~10−3 on large (>0.1 μm) grains. Allowing the grain equilibrium temperature to vary with grain size induces strong variations in relative ice abundances in low-density conditions in which the interstellar radiation field and in particular its ultraviolet component are not attenuated. Our study implies consequences not only for the initial formation of ices preceding the starless core stage, but also for the relative ice abundances on the grain populations going into the protostellar stage. In particular, if the smallest grains can lose their mantles owing to grain-grain collisions as the core is collapsing, the ice composition in the beginning of the protostellar stage could be very different than in the pre-collapse phase because the ice composition depends strongly on the grain size.

Carbon isotopic fractionation in molecular clouds

Context. Carbon fractionation has been studied from a theoretical point of view with different models of time-dependent chemistry, including both isotope-selective photodissociation and low-temperature isotopic exchange reactions. Aims. Recent chemical models predict that isotopic exchange reactions may lead to a depletion of 13C in nitrile-bearing species, with 12C/13C ratios two times higher than the elemental abundance ratio of 68 in the local interstellar medium. Since the carbon isotopic ratio is commonly used to evaluate the 14N/15N ratios with the double-isotope method, it is important to study carbon fractionation in detail to avoid incorrect assumptions. Methods. In this work, we implemented a gas-grain chemical model with new isotopic exchange reactions and investigated their introduction in the context of dense and cold molecular gas. In particular, we investigated the 12C/13C ratios of HNC, HCN, and CN using a grid of models, with temperatures and densities ranging from 10 to 50 K and 2 × 103 to 2 × 107 cm−3, respectively. Results. We suggest a possible 13C exchange through the 13C + C3 → 12C +13CC2 reaction, which does not result in dilution, but rather in 13C enhancement, for molecules that are formed starting from atomic carbon. This effect is efficient in a range of time between the formation of CO and its freeze-out on grains. Furthermore, the parameter-space exploration shows, on average, that the 12C/13C ratios of nitriles are predicted to be a factor 0.8–1.9 different from the local 12C/13C of 68 for high-mass star-forming regions. This result also affects the 14N/15N ratio: a value of 330 obtained with the double-isotope method is predicted to vary in the range 260–630, up to 1150, depending on the physical conditions. Finally, we studied the 12C/13C ratios of nitriles by varying the cosmic-ray ionisation rate, ζ: the 12C/13C ratios increase with ζ because of secondary photons and cosmic-ray reactions.

Interstellar glycolamide: A comprehensive rotational study and an astronomical search in Sgr B2(N).

Glycolamide is a glycine isomer and also one of the simplest derivatives of acetamide (e.g., one hydrogen atom is replaced with a hydroxyl group), which is a known interstellar molecule. In this context, the aim of our work is to provide direct experimental frequencies of the ground vibrational state of glycolamide in the centimeter-, millimeter- and submillimeter-wavelength regions in order to enable its identification in the interstellar medium. We employed a battery of state-of-the-art rotational spectroscopic techniques in the frequency and time domain to measure the frequencies of glycolamide. We used the spectral line survey named Exploring Molecular Complexity with ALMA (EMoCA), which was performed toward the star forming region Sgr B2(N) with ALMA to search for glycolamide in space. We also searched for glycolamide toward Sgr B2(N) with the Effelsberg radio telescope. The astronomical spectra were analyzed under the local thermodynamic equilibrium approximation. We used the gas-grain chemical kinetics model MAGICKAL to interpret the results of the astronomical observations. About 1500 transitions have been newly assigned up to 460 GHz to the most stable conformer, and a precise set of spectroscopic constants was determined. Spectral features of glycolamide were then searched for in the prominent hot molecular core Sgr B2(N2). We report the nondetection of glycolamide toward this source with an abundance at least six and five times lower than that of acetamide and glycolaldehyde, respectively. Our astrochemical model suggests that glycolamide may be present in this source at a level just below the upper limit, which was derived from the EMoCA survey. We could also not detect the molecule in the region's extended molecular envelope, which was probed with the Effelsberg telescope. We find an upper limit to its column density that is similar to the column densities obtained earlier for acetamide and glycolaldehyde with the Green Bank Telescope.

Sensitivity of gas-grain chemical models to surface reaction barriers

Context. The feasibility of contemporary gas-grain astrochemical models depends on the availability of accurate kinetics data, in particular, for surface processes. Aims. We study the sensitivity of gas-grain chemical models to the energy barrier Ea of the important surface reaction between some of the most abundant species: C and H2 (surface C + surface H2 → surface CH2). Methods. We used the gas-grain code ALCHEMIC to model the time-dependent chemical evolution over a 2D grid of densities (nH ∈ 103, 1012 cm−3) and temperatures (T ∈ 10, 300 K), assuming UV-dark (AV = 20 mag) and partly UV-irradiated (AV = 3 mag) conditions that are typical of the dense interstellar medium. We considered two values for the energy barrier of the surface reaction, Ea = 2500 K (as originally implemented in the networks) and Ea = 0 K (as measured in the laboratory and computed by quantum chemistry simulations). Results. We find that if the C + H2 → CH2 surface reaction is barrierless, a more rapid conversion of the surface carbon atoms into methane ice occurs. Overproduction of the CHn hydrocarbon ices affects the surface formation of more complex hydrocarbons, cyanides and nitriles, and CS-bearing species at low temperatures ≲10−15 K. The surface hydrogenation of CO and hence the synthesis of complex (organic) molecules become affected as well. As a result, important species whose abundances may change by more than a factor of two at 1 Myr include atomic carbon, small mono-carbonic (C1) and di-carbonic (C2) hydrocarbons, CO2, CN, HCN, HNC, HNCO, CS, H2CO, H2CS, CH2CO, and CH3OH (in either gas and/or ice). The abundances of key species, CO, H2O, and N2 as well as O, HCO+, N2H+, NH3, NO, and most of the S-bearing molecules, remain almost unaffected. Conclusions. Further accurate laboratory measurements and quantum chemical calculations of the surface reaction barriers will be crucial to improve the accuracy of astrochemical models.

Three-dimensional Projection Effects on Chemistry in a Planck Galactic Cold Clump

Abstract Offsets of molecular line emission peaks from continuum peaks are very common but frequently difficult to explain with a single spherical cloud chemical model. We propose that the spatial projection effects of an irregular three-dimensional (3D) cloud structure can be a solution. This work shows that the idea can be successfully applied to the Planck cold clump G224.4-0.6 by approximating it with four individual spherically symmetric cloud cores whose chemical patterns overlap with each other to produce observable line maps. With the empirical physical structures inferred from the observation data of this clump and a gas-grain chemical model, the four cores can satisfactorily reproduce its 850 μm continuum map and the diverse peak offsets of CCS, HC3N, and N2H+ simultaneously at chemical ages of about 8 × 105 ∼ 3 × 106 yr. The 3D projection effects on chemistry has the potential to explain such asymmetrical distributions of chemicals in many other molecular clouds.

Re-exploring Molecular Complexity with ALMA (ReMoCA): interstellar detection of urea

Context. Urea, NH2C(O)NH2, is a molecule of great importance in organic chemistry and biology. Two searches for urea in the interstellar medium have been reported in the past, but neither were conclusive. Aims. We want to take advantage of the increased sensitivity and angular resolution provided by the Atacama Large Millimeter/submillimeter Array (ALMA) to search for urea toward the hot molecular cores embedded in the high-mass-star-forming region Sgr B2(N). Methods. We used the new spectral line survey named ReMoCA (Re-exploring Molecular Complexity with ALMA) that was performed toward Sgr B2(N) with ALMA in its observing cycle 4 between 84 and 114 GHz. The spectra were analyzed under the local thermodynamic equilibrium approximation. We constructed a full synthetic spectrum that includes all the molecules identified so far. We used new spectroscopic predictions for urea in its vibrational ground state and first vibrationally excited state to search for this complex organic molecule in the ReMoCA data set. We employed the gas-grain chemical kinetics model MAGICKAL to interpret the astronomical observations. Results. We report the secure detection of urea toward the hot core Sgr B2(N1) at a position called N1S slightly offset from the continuum peak, which avoids obscuration by the dust. The identification of urea relies on nine clearly detected transitions. We derive a column density of 2.7 × 1016 cm−2 for urea, two orders of magnitude lower than the column density of formamide, and one order of magnitude below that of methyl isocyanate, acetamide, and N-methylformamide. The latter molecule is reliably identified toward N1S with 60 clearly detected lines, confirming an earlier claim of its tentative interstellar detection. We report the first interstellar detections of NH2CH18O and 15NH2CHO. We also report the nondetection of urea toward the secondary hot core Sgr B2(N2) with an abundance relative to the other four species at least one order of magnitude lower than toward the main hot core. Our chemical model roughly reproduces the relative abundances of formamide, methyl isocyanate, acetamide, and N-methylformamide, but it overproduces urea by at least one order of magnitude. Conclusions. Urea is clearly detected in one of the hot cores. Comparing the full chemical composition of Sgr B2(N1S) and Sgr B2(N2) may help understand why urea is at least one order of magnitude less abundant in the latter source.