Previous radio observations revealed widespread gas-phase methanol (CH$_3$OH) in the Central Molecular Zone (CMZ) at the Galactic center (GC), but its origin remains unclear. Here, we report the discovery of CH$_3$OH ice toward a star in the CMZ, based on a Subaru $3.4$-$4.0\ μ$m spectrum, aided by NASA/IRTF $L'$ imaging and $2$-$4\ μ$m spectra. The star lies $\sim8000$ au away in projection from a massive young stellar object (MYSO). Its observed high CH$_3$OH ice abundance ($17\%\pm3\%$ relative to H$_2$O ice) suggests that the $3.535\ μ$m CH$_3$OH ice absorption likely arises in the MYSO's extended envelope. However, it is also possible that CH$_3$OH ice forms with a higher abundance in dense clouds within the CMZ, compared to within the disk. Either way, our result implies that gas-phase CH$_3$OH in the CMZ can be largely produced by desorption from icy grains. The high solid CH$_3$OH abundance confirms the prominent $15.4\ μ$m shoulder absorption observed toward GC MYSOs arises from CO$_2$ ice mixed with CH$_3$OH.
Methanol and complex organic molecules have been found in cold starless cores, where a standard warm-up scenario would not work because of the absence of heat sources. A recent chemical model attributed the presence of methanol and large organics to the efficient chemical desorption and a class of neutral-neutral reactions that proceed fast at low temperatures in the gas phase. The model calls for a high abundance of methanol ice at the edge of the CO freeze-out zone in cold cloud cores. We performed medium resolution spectroscopy toward 3 field stars behind the starless core L1544 at 3 $μ$m t…
Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -- 14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10$^{-5}$ molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower ($<$ 10$^{-6}$ molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the o…
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…
Methanol Formation via the Radical-radical Reaction of OH and CH3 Radicals Undergoing Transient Diffusion on Ice at 10 to 60 K
Institute of Low Temperature Science, Hokkaido University（北海道大学低温科学研究所）；Komaba Institute for Science and Department of Basic Science, The University of Tokyo（东京大学理学院基础科学系）
Water in outflows from protostars originates either as a result of gas-phase synthesis from atomic oxygen at T > 200 K, or from sputtered ice mantles containing water ice. We aim to quantify the contribution of the two mechanisms that lead to water in outflows, by comparing observations of gas-phase water to methanol (a grain surface product) towards three low-mass protostars in NGC1333. In doing so, we also quantify the amount of methanol destroyed in outflows. To do this, we make use of JCMT and Herschel-HIFI data of H2O, CH3OH and CO emission lines and compare them to RADEX non-LTE excitati…
Methanol is a common component of interstellar and circumstellar ice mantles and is often used as an evolution indicator in star-forming regions. The observations of gas-phase methanol in the interiors of dense molecular clouds at temperatures as low as 10 K suggests that a non-thermal ice desorption must be active. Ice photodesorption was proposed to explain the abundances of gas-phase molecules toward the coldest regions. Laboratory experiments were performed to investigate the potential photodesorption of methanol toward the coldest regions. Solid methanol was deposited at 8 K and UV-irradi…
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…
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…
Broadband infrared spectroscopy of methanol isotopologues in pure, H2O-rich, and CO-rich ice analogues
Max-Planck-Institut für extraterrestrische Physik（马克斯·普朗克地外物理学研究所）；University of Kent（肯特大学）；HUN-REN Institute for Nuclear Research (Atomki)（匈牙利研究与教育网络核物理研究所）；INAF - Osservatorio Astrofisico di Catania（意大利国家天体物理研究所卡塔尼亚天文台）
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…
The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. CH4, O2, and hydrogen atoms are co-deposited i…
Backlighting young stellar objects in the Central Molecular Zone: an ensemble-averaged abundance structure of methanol ices
Ewha Womans University（梨花女子大学）；University of Hawaii（夏威夷大学）；Korea Astronomy and Space Science Institute（韩国天文与空间科学研究所）；University of Science and Technology, Korea (UST)（韩国科学技术院）
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…
Cold cores are an early step of star formation, characterized by densities > 10$^4$ cm$^{-3}$, low temperatures (< 15 K), and very low external UV radiation. We investigate the physico-chemical processes at play to tracing the origin of molecules that are predominantly formed via reactions on dust grain surfaces. We observed the cold core LDN 429-C with the NOEMA interferometer and the IRAM 30m single dish telescope in order to obtain the gas-phase abundances of key species, including CO and CH$_3$OH. Comparing the observed gas phase of methanol to its solid phase previously observed with Spit…
Chemical models predict that in cold cores gas-phase methanol is expected to be abundant at the outer edge of the CO depletion zone, where CO is actively adsorbed. CO adsorption correlates with volume density in cold cores, and, in nearby molecular clouds, the catastrophic CO freeze-out happens at volume densities above 10$^4$ cm$^{-3}$. The methanol production rate is maximized there and its freeze-out rate does not overcome its production rate, while the molecules are shielded from UV destruction by gas and dust. Thus, in cold cores, methanol abundance should generally correlate with visual …
Methanol (CH$_3$OH) is found to be abundant and widespread towards the Central Molecular Zone, the inner few hundred parsecs of our Galaxy. Its origin is, however, not fully understood. It was proposed that the high cosmic ray ionisation rate in this region could lead to a more efficient non-thermal desorption of this species formed on grain surfaces, but it would also mean that this species is destroyed in a relatively short timescale. In a first step, we run chemical models with a high cosmic ray ionisation rate and find that this scenario can only reproduce the lowest abundances of methanol…
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…
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…
Chemical models and experiments indicate that interstellar dust grains and their ice mantles play an important role in the production of complex organic molecules (COMs). To date, the most complex solid-phase molecule detected with certainty in the ISM is methanol, but the James Webb Space Telescope (JWST) may be able to identify still larger organic species. In this study, we use a coupled chemo-dynamical model to predict new candidate species for JWST detection toward the young star-forming core Cha-MMS1, combining the gas-grain chemical kinetic code MAGICKAL with a 1-D radiative hydrodynami…
Recent observations indicate that organic molecules are prevalent towards starless and prestellar cores. Deuteration of these molecules has not been well-studied during the starless phase. Published observations of singly-deuterated methanol, CH$_2$DOH, have only been observed in a couple of well-studied, dense and evolved prestellar cores (e.g. L1544, L183). Since the formation of gas-phase methanol during this cold phase is believed to occur via desorption from the icy grain surfaces, observations of CH$_2$DOH may be useful as a probe of the deuterium fraction in the ice mantles of dust grai…
Context. "Snow lines", marking regions where abundant volatiles freeze out onto the surface of dust grains, play an important role for planet growth and bulk composition in protoplanetary disks. They can already be observed in the envelopes of the much younger, low-mass Class 0 protostars that are still in their early phase of heavy accretion. Aims. We aim at using the information on the sublimation regions of different kinds of ices to understand the chemistry of the envelope, its temperature and density structure, and the history of the accretion process. Methods. As part of the CALYPSO IRAM…
Context. The molecular composition of interstellar ice mantles is defined by gas-grain processes in molecular clouds, with the main components being $H_2O$, $CO$, and $CO_2$. $CH_3OH$ ice is detected towards the denser regions, where large amounts of $CO$ freeze out and get hydrogenated. Heating from nearby protostars can further change the ice structure and composition. Despite the several observations of icy features towards molecular clouds and along the line of site of protostars, it is not yet clear if interstellar ices are mixed or if they have a layered structure. Aims. We aim to examin…
We present new radio-frequency interferometric maps of emission from the 14NH3, 15NH3, and 14NH2D isotopologues of ammonia, and the 12CH3OH and 13CH3OH isotopologues of methanol toward Sgr B2(N). With a resolution of ~3'' (0.1 pc), we are able to spatially resolve emission from two hot cores in this source and separate it from absorption against the compact HII regions in this area. The first (N1) is the well-known v = 64 km/s core, and the second (N2) is a core 6'' to the north at v = 73 km/s. Using emission from 15NH3, and hyperfine satellites of 14NH3 metastable transitions we estimate the …
The interaction between dust, ice, and gas during the formation of stars produces complex organic molecules. While observations indicate that several species are formed on ice-covered dust grains and are released into the gas phase, the exact chemical interplay between solid and gas phases and their relative importance remain unclear. Our goal is to study the interplay in regions of low-mass star formation through ice- and gas-mapping and by directly measuring gas-to-ice ratios. This provides constraints on the routes that lead to the chemical complexity that is observed in both phases. We pre…
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…
Under cold conditions in dense cores, gas-phase molecules and atoms are depleted from the gas-phase to the surface of interstellar grains. Considering the time scales and physical conditions within these cores, a portion of these molecules has to be brought back into the gas-phase to explain their observation by milimeter telescopes. We tested the respective efficiencies of the different mechanisms commonly included in the models. We also tested the addition of sputtering of ice grain mantles via a collision with cosmic rays in the electronic stopping power regime. The ice sputtering induced b…
Magnetic fields play an important role during star formation. Direct magnetic field strength observations have proven specifically challenging in the extremely dynamic protostellar phase. Because of their occurrence in the densest parts of star forming regions, masers, through polarization observations, are the main source of magnetic field strength and morphology measurements around protostars. Of all maser species, methanol is one of the strongest and most abundant tracers of gas around high-mass protostellar disks and in outflows. However, as experimental determination of the magnetic chara…
Methanol (CH$_3$OH) is at the root of organic ice chemistry in protoplanetary disks. However, its weak emission has made detections difficult. To date, gas-phase CH$_3$OH has been detected in only one Class II disk, TW Hya. We use the Atacama Large Millimeter/submillimeter Array (ALMA) to search for a total of four CH$_3$OH emission lines in bands 6 and 7 toward the disk around the young Herbig Ae star HD 163296. The disk-averaged column density of methanol and its related species formaldehyde (H$_2$CO) are estimated assuming optically thin emission in local thermodynamic equilibrium. We compa…
High-resolution mid-IR spectroscopy of SVS 13-A with EXES/SOFIA: The surprisingly high CH$_3$OH/H$_2$O ratio in the planet-forming zone of a solar mass protostar
Space Science Institute（空间科学研究所）；ESO（欧洲南方天文台）；INAF, Osservatorio Astrofisico di Arcetri（意大利国家天体物理研究所阿切特里天文台）；Univ. Grenoble Alpes, CNRS, IPAG（格勒诺布尔阿尔卑斯大学、法国国家科学研究中心、行星与地球物理研究所）；Space Science and Astrobiology Division, NASA Ames Research Center（美国宇航局艾姆斯研究中心空间科学与天体生物学部门）；Bay Area Environmental Research Institute（湾区环境研究所）；Jet Propulsion Laboratory, California Institute of Technology（加州理工学院喷气推进实验室）；Universitat Autònoma de Barcelona（巴塞罗那自治大学）；University of Turin（都灵大学）
The abundance of deuterated molecules in a star-forming region is sensitive to the environment in which they are formed. Deuteration fractions therefore provide a powerful tool for studying the physical and chemical evolution of a star-forming system. While local low-mass star-forming regions show very high deuteration ratios, much lower fractions are observed towards Orion and the Galactic Centre. We derive methanol deuteration fractions at a number of locations towards the high-mass star-forming region NGC 6334I, located at a mean distance of 1.3 kpc, and discuss how these can shed light on …
We study the effects of grain surface reactions on the chemistry of protoplanetary disks where gas, ice surface layers and icy mantles of dust grains are considered as three distinct phases. Gas phase and grain surface chemistry is found to be mainly driven by photo-reactions and dust temperature gradients. The icy disk interior has three distinct chemical regions: (i) the inner midplane with low FUV fluxes and warm dust ($\gtrsim 15$K) that lead to the formation of complex organic molecules, (ii) the outer midplane with higher FUV from the ISM and cold dust where hydrogenation reactions domin…
Computational models of interstellar gas-grain chemistry have historically adopted a single dust-grain size of 0.1 micron, assumed to be representative of the size distribution present in the interstellar medium. Here, we investigate the effects of a broad grain-size distribution on the chemistry on dust-grain surfaces and the subsequent build-up of molecular ices on the grains, using a three-phase gas-grain chemical model of a quiescent dark cloud. We include an explicit treatment of the grain temperatures, governed both by the visual extinction of the cloud and the size of each individual gr…
An important tracer of the origin and evolution of cometary ices is the comparison with ices found in dense clouds and towards Young Stellar Objects (YSOs). We present a survey of ices in the 2-5 micron spectra of 23 massive YSOs, taken with the NASA InfraRed Telescope Facility SpeX spectrometer. The 4.90 micron absorption band of OCS ice is detected in 20 sight-lines, more than five times the previously known detections. The absorption profile shows little variation and is consistent with OCS being embedded in CH3OH-rich ices, or proton-irradiated H$_2$S or SO$_2$-containing ices. The OCS col…
Carbon monoxide (CO) is the second most abundant molecule in the gas-phase of the interstellar medium. In dense molecular clouds, it is also present in the solid-phase as a constituent of the mixed water-dominated ices covering dust grains. Its presence in the solid-phase is inferred from its infrared (IR) signals. In experimental observations of solid CO/water mixed samples, its IR frequency splits into two components, giving rise to a blue- and a redshifted band. However, in astronomical observations, the former has never been observed. Several attempts have been carried out to explain this …
We investigate the chemistry in a radiation-hydrodynamics model of star-forming core which evolves from a cold ($\sim 10$ K) prestellar core to the main accretion phase in $\sim 10^5$ yr. A rotationally-supported gravitationally unstable disk is formed around a protostar. We extract the temporal variation of physical parameters in $\sim 1.5 \times 10^3$ SPH particles which end up in the disk, and perform post-processing calculations of the gas-grain chemistry adopting a three-phase model. Inside the disk, the SPH particles migrate both inward and outward. Since a significant fraction of volati…
We present an extensive review of gas phase reactions producing methylacetylene and propene showing that these relatively abundant unsaturated hydrocarbons cannot be synthesized through gas-phase reactions. We explain the formation of propene and methylacetylene through surface hydrogenation of C3 depleted onto interstellar ices, C3 being a very abundant species in the gas phase.
Methanol and formaldehyde are two simple organic molecules that are ubiquitously detected in the interstellar medium. An origin in the solid phase and a subsequent nonthermal desorption into the gas phase is often invoked to explain their abundances in some of the environments where they are found. Experimental simulations under astrophysically relevant conditions have been carried out to find a suitable mechanism for that process. We explore the in situ formation and subsequent photon-induced desorption of these species, studying the UV photoprocessing of pure ethanol ice, and a more realisti…
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$_{…
Complex organic molecules (COMs), which are the seeds of prebiotic material and precursors of amino acids and sugars, form in the icy mantles of circumstellar dust grains but cannot be detected remotely unless they are heated and released to the gas phase. Around solar-mass stars, water and COMs only sublimate in the inner few au of the disk, making them extremely difficult to spatially resolve and study. Sudden increases in the luminosity of the central star will quickly expand the sublimation front (so-called snow line) to larger radii, as seen previously in the FU Ori outburst of the young …
