The chemical network governing interstellar sulfur has been the topic of unrelenting discussion for the past decades due to the conspicuous discrepancy between its expected and observed abundances in different interstellar environments. More recently, the astronomical detections of CH3CH2SH and CH2CS highlighted the importance of interstellar formation routes for sulfur-bearing organic molecules with two carbon atoms. In this work, we perform a laboratory investigation of the solid-state chemistry resulting from the interaction between C2H2 molecules and SH radicals -- both thought to be present in interstellar icy mantles -- at 10 K. Reflection absorption infrared spectroscopy and quadrupole mass spectrometry combined with temperature-programmed desorption experiments are employed as analytical techniques. We confirm that SH radicals can kick-start a sulfur reaction network under interstellar cloud conditions and identify at least six sulfurated products: CH3CH2SH, CH2CHSH, HSCH2CH2SH, H2S2, and tentatively CH3CHS and CH2CS. Complementarily, we utilize computational calculations to pinpoint the reaction routes that play a role in the chemical network behind our experimental results. The main sulfur-bearing organic molecule formed under our experimental conditions is CH3CH2SH and its formation yield increases with the ratios of H to other reactants. It serves as a sink to the sulfur budget within the network, being formed at the expense of the other unsaturated products. The astrophysical implications of the chemical network proposed here are discussed.
Observations carried out toward starless and pre-stellar cores have revealed that complex organic molecules are prevalent in these objects, but it is unclear what chemical processes are involved in their formation. Recently, it has been shown that complex organics are preferentially produced at an intermediate-density shell within the L1544 pre-stellar core at radial distances of ~4000 au with respect to the core center. However, the spatial distribution of complex organics has only been inferred toward this core and it remains unknown whether these species present a similar behaviour in other…
We present an unbiased spectral line survey toward the Galactic Centre (GC) quiescent giant molecular cloud (QGMC), G+0.693 using the GBT and IRAM 30$\,$ telescopes. Our study highlights an extremely rich organic inventory of abundant amounts of nitrogen (N)-bearing species in a source without signatures of star formation. We report the detection of 17 N-bearing species in this source, of which 8 are complex organic molecules (COMs). A comparison of the derived abundances relative to H$_2$ is made across various galactic and extragalactic environments. We conclude that the unique chemistry in …
We report the detection of the oxygen-bearing complex organic molecules propenal (C2H3CHO), vinyl alcohol (C2H3OH), methyl formate (HCOOCH3), and dimethyl ether (CH3OCH3) toward the cyanopolyyne peak of the starless core TMC-1. These molecules are detected through several emission lines in a deep Q-band line survey of TMC-1 carried out with the Yebes 40m telescope. These observations reveal that the cyanopolyyne peak of TMC-1, which is the prototype of cold dark cloud rich in carbon chains, contains also O-bearing complex organic molecules like HCOOCH3 and CH3OCH3, which have been previously s…
It is not known whether the original carriers of Earth's nitrogen were molecular ices or refractory dust. To investigate this question, we have used data and results of Herschel observations towards two protostellar sources: the high-mass hot core of Orion KL, and the low-mass protostar IRAS 16293-2422. Towards Orion KL, our analysis of the molecular inventory of Crockett et al. (2014) indicates that HCN is the organic molecule that contains by far the most nitrogen, carrying $74_{-9}^{+5}\%$ of nitrogen-in-organics. Following this evidence, we explore HCN towards IRAS 16293-2422, which we con…
Formation of N-bearing complex organic molecules in molecular clouds: Ketenimine, acetonitrile, acetaldimine, and vinylamine via the UV photolysis of C$_2$H$_2$ ice
(Abridged) Gas-phase complex organic molecules are commonly detected in the warm inner regions of protostellar envelopes. Recent models show that photochemistry in ices followed by desorption may explain the observed abundances. This study aims to experimentally quantify the broad-band UV-induced production rates of complex organics in CH3OH-rich ices at 20-70 K under ultra-high vacuum conditions. The reaction products are mainly identified by RAIRS and TPD experiments. Complex organics are readily formed in all experiments, both during irradiation and during a slow warm-up of the ices to 200 …
Interstellar ice mantles on the surfaces of dust grains are thought to have a bi-layered structure, with a H2O-rich polar layer, covered by a CO-rich apolar layer that probably harbors H2 and other volatiles such as N2. In this work, we explore the chemistry induced by 2 keV electrons and Ly-alpha photons in H2:CO:15N2 ice analogs of the CO-rich layer when exposed to similar fluences to those expected from the cosmic-ray-induced secondary electrons and UV photons during the typical lifetime of dense clouds. Six products were identified upon 2 keV electron irradiation: CO2, C2O (and other carbo…
Isolated dense molecular cores are investigated to study the onset of complex organic molecule formation in interstellar ice. Sampling three cores with ongoing formation of low-mass stars (B59, B335, and L483) and one starless core (L694-2) we sample lines of sight to nine background stars and five young stellar objects (YSOs; A_K ~0.5 - 4.7). Spectra of these stars from 2-5 $μ$m with NASA's Infrared Telescope Facility (IRTF) simultaneously display signatures from the cores of H$_2$O (3.0 $μ$m), CH$_3$OH (C-H stretching mode, 3.53 $μ$m) and CO (4.67 $μ$m) ices. The CO ice is traced by nine sta…
Recent observations have shown that Nitrogen-bearing complex organic species are present in large quantities in star-forming regions. Thus, investigating the N-bearing species in a hot molecular core, such as G10.47+0.03, is crucial to understanding the molecular complexity in star-forming regions. They also allow us to investigate the chemical and physical processes that determine the many phases during the structural and chemical evolution of the source in star-forming regions. The aim of this study is to investigate the spatial distribution and the chemical evolution states of N-bearing com…
The chemical inventory of planets is determined by the physical and chemical processes that govern the early phases of star formation. The aim is to investigate N-bearing complex organic molecules towards two Class 0 protostars (B1-c and S68N) at millimetre wavelengths with ALMA. Next, the results of the detected N-bearing species are compared with those of O-bearing species for the same and other sources. ALMA observations in Band 6 ($\sim$ 1 mm) and Band 5 ($\sim$ 2 mm) are studied at $\sim$ 0.5" resolution, complemented by Band 3 ($\sim$ 3 mm) data in a $\sim$ 2.5" beam. NH2CHO, C2H5CN, HNC…
Molecule-dependent Abundance Behavior of Oxygen-bearing Complex Organics in High-Mass Star-Forming Regions: A Uniform 50-source Survey
Chongqing University（重庆大学）；Shenzhen Technology University（深圳职业技术大学）；Guangxi University（广西大学）；Xi’an Jiaotong-Liverpool University（西交利物浦大学）；Tsinghua University（清华大学）；National Astronomical Observatories, Chinese Academy of Sciences（中国科学院国家天文台）；Observatoire de Paris, PSL Research University, CNRS, Sorbonne Universités（巴黎天文台、PSL研究大学、法国国家科学研究中心、索邦大学）
To explain the properties of dust in the interstellar medium (ISM), the presence of a refractory organic mantle is necessary. The outflows of AGB stars are among the main contributors of stellar dust to the ISM. We present the first study of the refractory organic contribution of AGB stars to the ISM. Based on laboratory experiments, we included a new reaction in our extended chemical kinetics model: the photoprocessing of volatile complex ices into inert refractory organic material. The refractory organic feedback of AGB outflows to the ISM is estimated using observationally motivated parent …
In cold core of dark molecular clouds, where the UV radiation from external sources is strongly attenuated, cosmic rays can induce chemical reactions on the surface of ice-covered grains promoting the ejection of the processed material to the gas phase. We report the positive and negative secondary ion emission from pure CH3CN, C2H3CN and i-C3H7CN ices due to the bombardment of heavy ions (252Cf fission fragments), simulating the incidence of cosmic rays onto icy surfaces. The secondary ions emitted from each sample were analysed by time-of-flight mass spectrometry (TOF-MS), using Plasma Desor…
Since the start of ALMA observatory operation, new and important chemistry of infrared cold core was revealed. Molecular transitions at millimeter range are being used to identify and to characterize these sources. We have investigated the 231 GHz ALMA archive observations of the infrared dark cloud region C9, focusing on the brighter source that we called as IRDC-C9 Main. We report the existence of two sub-structures on the continuum map of this source: a compact bright spot with high chemistry diversity that we labelled as core, and a weaker and extended one, that we labelled as tail. In the…
We present chemical implications arising from spectral models fit to the Herschel/HIFI spectral survey toward the Orion Kleinmann-Low nebula (Orion KL). We focus our discussion on the eight complex organics detected within the HIFI survey utilizing a novel technique to identify those molecules emitting in the hottest gas. In particular, we find the complex nitrogen bearing species CH$_{3}$CN, C$_{2}$H$_{3}$CN, C$_{2}$H$_{5}$CN, and NH$_{2}$CHO systematically trace hotter gas than the oxygen bearing organics CH$_{3}$OH, C$_{2}$H$_{5}$OH, CH$_{3}$OCH$_{3}$, and CH$_{3}$OCHO, which do not contain…
Ionization of gas-phase organic molecules such as polycyclic aromatic hydrocarbons (PAHs) requires vacuum ultraviolet photons at wavelengths shorter than 200 nm (~6-9 eV). We present here for the first time that visible photons - accessible through sunlight - can cause photoionization of trapped PAHs in cryogenic water-ice, accounting for 4.4 eV less ionization energy than in the gas phase. This finding opens up new reaction pathways involving low-energy ionization in many environments where water and organic matter coexist. This include the interstellar medium, molecular clouds, protoplanetar…
Modeling the UV-photon irradiation of CS$_2$-bearing ices in the laboratory with the pyRate gas-grain astrochemical code. New insights into the missing sulfur problem
Max-Planck-Institut für Extraterrestrische Physik (MPE)（马克斯·普朗克地外物理研究所）；Centro de Astrobiología (CSIC-INTA)（天体生物学中心（西班牙国家科学技术研究委员会-国家航空航天技术研究所））
Complex organic molecules (COMs) are thought to form on icy dust grains in the earliest phase of star formation. The evolution of these COMs from the youngest Class 0/I protostellar phases toward the more evolved Class II phase is still not fully understood. Since planet formation seems to start early, and mature disks are too cold for characteristic COM emission lines, studying the inventory of COMs on solar system scales in the Class 0/I stage is relevant. ALMA Band 3 (3 mm) and Band 6 (1 mm) observations are obtained of seven Class 0 protostars in the Perseus and Serpens star-forming region…
Methanol ice is embedded in interstellar ice mantles present in dense molecular clouds. We aim to measure the sputtering efficiencies starting from different ice mantles of varying compositions experimentally, in order to evaluate their potential impact on astrochemical models. The sputtering yields of complex organic molecules is of particular interest, since few mechanisms are efficient enough to induce a significant feedback to the gas phase. We irradiated methanol and carbon dioxide ice mixtures of varying ratios with swift heavy ions in the electronic sputtering regime. We monitored the e…
The increasing sensitivity and resolution of ground-based telescopes have enabled the detection of gas-phase complex organic molecules (COMs) across a variety of environments. Many of the detected species are expected to form on the icy surface of interstellar grains and transfer later into the gas phase. Therefore, icy material is regarded as a primordial source of COMs in the ISM. Upcoming JWST observations of interstellar ices in star-forming regions will reveal IR features of frozen molecules with unprecedented resolution and sensitivity. To identify COM features in the JWST data, lab IR s…
Laboratory experiments have confirmed that the radiolytic decay rate of astrochemical ice analogues is dependent upon the solid phase of the target ice, with some crystalline molecular ices being more radio-resistant than their amorphous counterparts. The degree of radio-resistance exhibited by crystalline ice phases is dependent upon the nature, strength, and extent of the intermolecular interactions that characterise their solid structure. For example, it has been shown that crystalline CH3OH decays at a significantly slower rate when irradiated by 2 keV electrons at 20 K than does the amorp…
Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. We aim at experimentally measuring X-ray photodesorption yields of methanol and its photo-products from binary mixed ices: $^{13}$CO:CH$_3$OH ice and H$_2$O…
We investigate the chemical segregation of complex O-bearing species (including the largest and most complex ones detected to date in space) towards Orion KL, the closest high-mass star-forming region. The molecular line images obtained using the ALMA science verification data reveal a clear segregation of chemically related species depending on their different functional groups. We map the emission of 13CH3OH, HCOOCH3, CH3OCH3, CH2OCH2, CH3COOCH3, HCOOCH2CH3, CH3CH2OCH3, HCOOH, OHCH2CH2OH, CH3COOH, CH3CH2OH, CH3OCH2OH, OHCH2CHO, and CH3COCH3 with 1.5" angular resolution and provide molecular …
We study the chemical evolution of H2O:CO:NH3 ice mixtures irradiated with soft X-rays, in the range 250-1250 eV. We identify many nitrogen-bearing molecules such as e.g., OCN-, NH4+ , HNCO, CH3CN, HCONH2, and NH2COCONH2. Several infrared features are compatible with glycine or its isomers. During the irradiation, we detected through mass spectroscopy many species desorbing the ice. Such findings support either the infrared identifications and reveal less abundant species with not clear infrared features. Among them, m/z = 57 has been ascribed to methyl isocyanate (CH3NCO), a molecule of prebi…
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 mol…
Based on astrochemical theory, the complex molecular composition around high-mass YSOs should evolve from the outer envelope in toward the central hot region as a sequence of temperature dependent chemical pathways are activated in ices and in the gas-phase. The resulting complex molecules have been broadly classified into three generations dependent on the temperature (<25, >25, and >100 K) required for formation. We combine IRAM 30m and Submillimeter Array observations to explore the spatial distribution of organic molecules around the high-mass young stellar object NGC 7538 IRS9, whose weak…
The design, implementation, and performance of a customized carbon atom beam source for the purpose of investigating solid-state reaction routes in interstellar ices in molecular clouds are discussed. The source is integrated into an existing ultrahigh vacuum setup, SURFace REaction SImulation DEvice (SURFRESIDE$^{2}$), which extends this double atom (H/D, O, and N) beamline apparatus with a third atom (C) beamline to a unique system that is fully suited to explore complex organic molecule solid-state formation under representative interstellar cloud conditions. The parameter space for this sy…
Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking. Aims. This work provides infrared reference spectra of acetaldehyde (CH$_3$CHO), ethanol (CH$_3$CH$_2$OH), and di…
Large interstellar organic molecules are potential precursors of prebiotic molecules. Their formation pathways and chemical relationships with one another and simpler molecules are therefore of great interest. In this paper, we address the relationship between two classes of large organic molecules, carbon chains and saturated complex organic molecules (COMs), at the early stages of star formation through observations of C4H and CH3OH. We surveyed these molecules with the IRAM 30m telescope toward 16 deeply embedded low-mass protostars selected from the Spitzer c2d ice survey. We find that CH3…
Binding energies (BEs) are one of the most important parameters for astrochemical modeling determining, because they govern whether a species stays in the gas-phase or is frozen on the grain surfaces. It is currently known that, in the denser and colder regions of the interstellar medium, sulphur is severely depleted in the gas phase. It has been suggested that it may be locked into the grain icy mantles. However, which are the main sulphur carriers is still a matter of debate. This work aims at establishing accurate BEs of 17 sulphur-containing species on two validated water ice structural mo…
The occurrence of complex organic molecules (COMs) in the gas phase at low temperature in the dense phases of the ISM suggests that a non-thermal desorption mechanism is at work because otherwise, COMs should condense within a short timescale onto dust grains. Vacuum ultraviolet photodesorption has been shown to be much less efficient for complex organic molecules, such as methanol, because mostly photoproducts are ejected. The induced photolysis competes with photodesorption for large COMs, considerably lowering the efficiency to desorb intact molecules. We investigate the sputtering efficien…
Methanol and its precursor formaldehyde are among the most studied organic molecules in the interstellar medium and are abundant in the gaseous and solid phases. We recently developed a model to simulate CO hydrogenation via H atoms on interstellar ice surfaces, the most important interstellar route to H2CO and CH3OH, under laboratory conditions. We extend this model to simulate the formation of both organic species under interstellar conditions, including freeze-out from the gas and hydrogenation on surfaces. Our aim is to compare calculated abundance ratios with observed values and with the …
The interstellar medium is characterized by a rich and diverse chemistry. Many of its complex organic molecules are proposed to form through radical chemistry in icy grain mantles. Radicals form readily when interstellar ices (composed of water and other volatiles) are exposed to UV photons and other sources of dissociative radiation, and, if sufficiently mobile, the radicals can react to form larger, more complex molecules. The resulting complex organic molecules (COMs) accompany star and planet formation, and may eventually seed the origins of life on nascent planets. Experiments of increasi…
The simultaneous detection of organic molecules of the form C$_2$H$_{\text{n}}$O, such as ketene (CH$_2$CO), acetaldehyde (CH$_3$CHO), and ethanol (CH$_3$CH$_2$OH), toward early star-forming regions offers hints of shared chemical history. Several reaction routes have been proposed and experimentally verified under various interstellar conditions to explain the formation pathways involved. Most noticeably, the non-energetic processing of C$_2$H$_2$ ice with OH-radicals and H-atoms was shown to provide formation routes to ketene, acetaldehyde, ethanol, and vinyl alcohol (CH$_2$CHOH) along the H…
Experimental and computational studies of the hydrogenation of carbon disulfide (CS2) on ice analogues
Institute of Low Temperature Science, Hokkaido University（北海道大学低温科学研究所）；Instituto de Fisica Fundamental, CSIC（西班牙国家科学研究理事会基础物理研究所）；Observatorio Astronómico Nacional (OAN)（国家天文台）；Observatorio de Yebes, IGN（伊耶韦斯天文台，国家地理研究所）
The different spatial distributions of N-bearing and O-bearing species, as is well known towards Orion~KL, is one of the long-lasting mysteries. We conducted a survey observation and chemical modeling study to investigate if the different distributions of O- and N-bearing species are widely recognized in general star-forming regions. First, we report our observational results of complex organic molecules (COMs) with the 45~m radio telescope at the Nobeyama Radio Observatory towards eight star-forming regions. Through our spectral survey ranging from 80 to 108~GHz, we detected CH$_3$OH, HCOOCH$…
Benzonitrile (c-C6H5CN) has been recently detected in cold and dense regions of the interstellar medium (ISM), where it has been used as a signpost of a rich aromatic organic chemistry that might lead to the production of polycyclic aromatic hydrocarbons (PAHs). One possible origin of this benzonitrile is interstellar ice chemistry involving benzene (c-C6H6) and nitrile molecules (organic molecules containing the -CN group). We have addressed the plausibility of this c-C6H5CN formation pathway through laboratory experiments using our new setup SPACE TIGER. The SPACE TIGER experimental setup is…
Context. Infrared spectroscopy of star and planet forming regions is at the dawn of a new age with the upcoming James Webb Space Telescope. In support of these observations, laboratory spectra are required to identify complex organic molecules in the ices that cover the dust grains in these regions. Aims. This study aims to provide reference spectra to firmly detect icy methyl formate in the different stages of star and planet forming regions. Methyl formate is mixed in astronomically relevant matrices, and the peak positions, FWHMs, and relative band intensities are characterized for differen…
Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high- mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules: methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH), through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO-…
We have observed the Class I protostellar source Elias 29 with Atacama Large Millimeter/submillimeter Array (ALMA). We have detected CS, SO, $^{34}$SO, SO$_2$, and SiO line emissions in a compact component concentrated near the protostar and a ridge component separated from the protostar by 4\arcsec\ ($\sim 500$ au). The former component is found to be abundant in SO and SO$_2$ but deficient in CS. The abundance ratio SO/CS is as high as $3^{+13}_{-2} \times 10^2$ at the protostar, which is even higher than that in the outflow-shocked region of L1157 B1. However, organic molecules (HCOOCH$_3$,…
No statistical study of COMs toward a large sample of high-mass protostars with ALMA has been carried out so far. We aim to study six N-bearing species: CH$_3$CN, HNCO, NH$_2$CHO, C$_2$H$_5$CN, C$_2$H$_3$CN and CH$_3$NH$_2$ in a large sample of high-mass protostars. From the ALMAGAL survey, 37 of the most line-rich hot molecular cores are selected. Next, we fit their spectra and find column densities and excitation temperatures of the above N-bearing species, in addition to CH$_3$OH. We (tentatively) detect CH$_3$NH$_2$ in $\sim32%$ of the sources. We find three groups of species when comparin…
