The aim of the presented work is to analyze the impact of experimentally evaluated reactions of hydrogen abstraction on surfaces of interstellar grains on the chemical evolution of methanol and its precursors on grains and in the gas phase under conditions of cold dark cloud and during the collapse of the translucent cloud into the dark cloud. Analysis of simulation results shows that those reactions are highly efficient destruction channels for HCO and H2CO on grain surfaces, and significantly impact the abundances of almost all molecules participating in the formation of CH3OH. Next, in models with those reactions maximum abundances of methanol in gas and on grain surface decrease by more than 2-3 orders of magnitude in comparison to models without surface abstraction reactions of hydrogen. Finally, we study the impact of binding energies of CH2OH and CH3O radicals on methanol chemistry.
The revised version of the class I methanol maser catalog is presented. It contains 198 sources - new class I methanol masers detected in the direction of EGOs were added to the previous number (~160 sources have been published in the first version of this catalog - see reference in the text). Electronic version has been generated in the form of html file - http://www.asc.rssi.ru/MMI A statistical analysis was carried out within 2' around a maser position to find an identification of class I methanol masers with any objects typical for star-forming regions - UCHII regions, IRAS sources, bipola…
The relative abundances of singly-deuterated methanol isotopologues, [CH$_{2}$DOH]/[CH$_{3}$OD], in star-forming regions deviate from the statistically expected ratio of 3. In Orion KL, the nearest high-mass star-forming region to Earth, the singly-deuterated methanol ratio is about 1, and the cause for this observation has been explored through theory for nearly three decades. We present high-angular resolution observations of Orion KL using the Atacama Large Millimeter/submillimeter Array to map small-scale changes in CH$_{3}$OD column density across the nebula, which provide a new avenue to…
The outer Galaxy is an environment with metallicity lower than the Solar one and, because of this, the formation and survival of molecules in star-forming regions located in the inner and outer Galaxy is expected to be different. To gain understanding on how chemistry changes throughout the Milky Way, it is crucial to observe outer Galaxy star-forming regions to constrain models adapted for lower metallicity environments. The project "chemical complexity in star-forming regions of the outer Galaxy" (CHEMOUT) aims to address this problem observing a sample of 35 high-mass star-forming cores at …
We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or non-existent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no tempera…
This study aims to elucidate a possible link between chemical properties of ices in star-forming regions and environmental characteristics of the host galaxy. We performed 3--4 micron spectroscopic observations toward nine embedded high-mass YSOs in the Large Magellanic Cloud (LMC) with the ISAAC at the VLT. Additionally, we analyzed archival ISAAC data of two LMC YSOs. As a result, we detected absorption bands due to solid H2O and CH3OH as well as the 3.47 micron absorption band. The 3.53 micron CH3OH ice absorption band for the LMC YSOs is found to be absent or very weak compared to that see…
We have carried out observations of CCH ($N=1-0$), CH$_{3}$CN ($J=5-4$), and three $^{13}$C isotopologues of HC$_{3}$N ($J=10-9$) toward three massive young stellar objects (MYSOs), G12.89+0.49, G16.86--2.16, and G28.28--0.36, with the Nobeyama 45-m radio telescope. Combined with previous results on HC$_{5}$N, the column density ratios of $N$(CCH)/$N$(HC$_{5}$N), hereafter the CCH/HC$_{5}$N ratios, in the MYSOs are derived to be $\sim 15$. This value is lower than that in a low-mass warm carbon chain chemistry (WCCC) source by more than one order of magnitude. We compare the observed CCH/HC$_{…
The recent detection of gas-phase methanol (CH$_3$OH) lines in the disc of TW Hya by Walsh et al. provided the first observational constraints on the complex O-bearing organic content in protoplanetary discs. The emission has a ring-like morphology, with a peak at $\sim 30-50$ au and an inferred column density of $\sim 3-6\times10^{12}$ cm$^{-2}$. A low CH$_3$OH fractional abundance of $\sim 0.3-4\times 10^{-11}$ (with respect to H$_2$) is derived, depending on the assumed vertical location of the CH$_3$OH molecular layer. In this study, we use a thermo-chemical model of the TW Hya disc, coupl…
Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of $^{15}$N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised $^{15}$N enrichments fail to match observed v…
In this paper we use observations of molecular tracers in metal rich and alpha-enhanced galaxies to study the effect of abundance changes on molecular chemistry. We selected a sample of metal rich spiral and star bursting objects from the literature, and present here new data for a sample of early-type galaxies (ETGs). We conducted the first survey of CS and methanol emission in ETGs, detecting 7 objects in CS, and 5 in methanol emission. We find evidence to support the hypothesis that CS is a better tracer of dense star-forming gas than HCN. We suggest that the methanol emission in these sour…
Electron irradiation and temperature-programmed desorption of layered ethanolamine-water-methanol ices
Zernike Institute for Advanced Materials, University of Groningen（格罗宁根大学泽尔尼克高级材料研究所）；Center for Astrochemical Studies, Max-Planck-Institut für Extraterrestrische Physik（马克斯·普朗克地外物理研究所天体化学研究中心）；Department of Bioscience, Technical University of Munich（慕尼黑工业大学生物科学系）；Síntesis y Mecanismos de Reacción en Química Orgánica, Departamento de Química, Universidad del Valle（瓦尔莱大学化学系有机化学反应合成与机理）；Semillero de investigación en Astroquímica y Astrobiología (AstroLUCA), Departamento de Química, Universidad del Valle（瓦尔莱大学化学系天体化学与天体生物学研究种子团队（AstroLUCA））；Faculty of Health Sciences, Universidad Libre（自由大学健康科学学院）；HUN-REN Institute for Nuclear Research（匈牙利研究与创新网络核子研究所）；Institute of Chemistry, University of Debrecen（德布勒森大学化学研究所）；Astronomical Institute, Slovak Academy of Sciences（斯洛伐克科学院天文研究所）
Mantles of iced water, mixed with CO, H2CO, and CH3OH are formed during the so called prestellar core phase. In addition, radicals are also thought to be formed on the grain surfaces, and to react to form complex organic molecules later on, during the warm-up phase of the protostellar evolution. We aim to study the formation of the grain mantles during the prestellar core phase and the abundance of H2CO, CH3OH, and radicals trapped in them. We have developed a macrosopic statistic multilayer model that follows the formation of grain mantles with time and that includes two effects that may incr…
Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. We present the detection of the Complex Organic Molecules (COMs) acetaldehyde and methyl formate as well as formic acid and ketene, and the tentative detection of di-methyl ether towards the methanol hots…
Gas-phase methanol was recently detected in a protoplanetary disk for the first time with ALMA. The peak abundance and distribution of methanol observed in TW Hya differed from that predicted by chemical models. Here, the chemistry of methanol gas and ice is calculated using a physical model tailored for TW Hya with the aim to contrast the results with the recent detection in this source. New pathways for the formation of larger complex molecules (e.g., ethylene glycol) are included in an updated chemical model, as well as the fragmentation of methanol ice upon photodesorption. It is found tha…
We present a model for the formation of large organic molecules in dark clouds. The molecules are produced in the high density gas-phase that exists immediately after ice mantles are explosively sublimated. The explosions are initiated by the catastrophic recombination of trapped atomic hydrogen. We propose that, in molecular clouds, the processes of freeze-out onto ice mantles, accumulation of radicals, explosion and then rapid (three-body) gas-phase chemistry occurs in a cyclic fashion. This can lead to a cumulative molecular enrichment of the interstellar medium. A model of the time-depende…
The Large and Small Magellanic Clouds (LMC and SMC), gas-rich dwarf companions of the Milky Way, are the nearest laboratories for detailed studies on the formation and survival of complex organic molecules (COMs) under metal poor conditions. To date, only methanol, methyl formate, and dimethyl ether have been detected in these galaxies - all three toward two hot cores in the N113 star-forming region in the LMC, the only extragalactic sources exhibiting complex hot core chemistry. We describe a small and diverse sample of the LMC and SMC sources associated with COMs or hot core chemistry, and c…
As the number of complex organic molecules (COMs) detected in the interstellar medium increases, it becomes important to place meaningful constraints on the formation pathways of these species. The molecular cloud SgrB2(N) is host to several hot molecular cores in the early stage of star formation, where a great variety of COMs are detected in the gas phase. Because of its exposure to the extreme conditions of the the Galactic center region, SgrB2(N) is one of the best targets to study the impact of environmental conditions on the production of COMs. Our main goal is to characterize the physic…
We present a study of emission lines of small hydrocarbons C$_2$H and $c$-C$_3$H$_2$, and COMs precursors H$_2$CO and CH$_3$OH in order to better understand the possible chemical link between the molecular abundances and UV radiation field in photodissociation regions (PDRs). We study two PDRs around extended and compact HII regions with $G \leq 50$~Habings in the S235 star-forming complex. We find the highest abundances of both hydrocarbons on the edges of molecular clumps, while $c$-C$_3$H$_2$ is also abundant in the low-density expanding PDR around compact HII region S235\,A. We see the hig…
Context. In dense clouds, hydrogenation reactions on icy dust grains are key in the formation of molecules, like formaldehyde, methanol, and complex organic molecules (COMs). These species form through the sequential hydrogenation of CO ice. Although molecular hydrogen (H2) abundances can be four orders of magnitude higher than those of free H-atoms in dense clouds, H2 surface chemistry has been largely ignored; several laboratory studies show that H2 does not actively participate in non-energetic ice chemistry because of the high activation energies required. Aims. For the example of CO ice h…
A magnetohydrodynamic model of a steady, transverse C-type shock in a dense molecular cloud is presented. A complete gas-grain chemical network is taken into account: the gas-phase chemistry, the adsorption of gas species on dust grains, various desorption mechanisms, the grain surface chemistry, the ion neutralization on dust grains, the sputtering of grain mantles. The population densities of energy levels of ions CI, CII and OI and molecules H$_2$, CO, H$_2$O are computed in parallel with the dynamical and chemical rate equations. The large velocity gradient approximation is used in the lin…
This review paper summarizes the state-of-the-art in laboratory based interstellar ice chemistry. The focus is on atom addition reactions, illustrating how water, carbon dioxide and methanol can form in the solid state at astronomically relevant temperatures, and also the formation of more complex species such as hydroxylamine, an important prebiotic molecule, and glycolaldehyde, the smallest sugar, is discussed. These reactions are particularly relevant during the dark ages of star and planet formation, i.e., when the role of UV light is restricted. A quantitative characterization of such pro…
Nitrogen bearing species are common tracers of the physical conditions in a wide variety of objects, and most remarkably in dark clouds. The reservoir of gaseous nitrogen is expected to be atomic or molecular, but none of the two species are observable in the dark gas. Their abundances therefore derive indirectly from those of N-bearing species through chemical modelling. The recent years have accumulated data which stress our incomplete understanding of the nitrogen chemistry in dark cloud conditions. To tackle this problem of the nitrogen chemistry in cold gas, we have revised the formation …
We present spectroscopic observations of a sample of 15 embedded young stellar objects (YSOs) in the Large Magellanic Cloud (LMC). These observations were obtained with the Spitzer Infrared Spectrograph (IRS) as part of the SAGE-Spec Legacy program. We analyze the two prominent ice bands in the IRS spectral range: the bending mode of CO_2 ice at 15.2 micron and the ice band between 5 and 7 micron that includes contributions from the bending mode of water ice at 6 micron amongst other ice species. The 5-7 micron band is difficult to identify in our LMC sample due to the conspicuous presence of …
(Abridged) Understanding the details of the formation process of massive (i.e. M<8-10M$_\odot$) stars is a long-standing problem in astrophysics. [...] We present a method to derive accurate timescales of the different evolutionary phases of the high-mass star formation process. We model a representative number of massive clumps of the ATLASGAL-TOP100 sample which cover all the evolutionary stages. The models describe an isothermal collapse and the subsequent warm-up phase, for which we follow their chemical evolution. The timescale of each phase is derived by comparing the results of the mode…
We investigate the formation and evolution of interstellar dust-grain ices under dark-cloud conditions, with a particular emphasis on CO2. We use a three-phase model (gas/surface/mantle) to simulate the coupled gas--grain chemistry, allowing the distinction of the chemically-active surface from the ice layers preserved in the mantle beneath. The model includes a treatment of the competition between barrier-mediated surface reactions and thermal-hopping processes. The results show excellent agreement with the observed behavior of CO2, CO and water ice in the interstellar medium. The reaction of…
