Methanol is the most complex molecule securely identified in interstellar ices and is a key chemical species for understanding chemical complexity in astrophysical environments. Important aspects of the methanol ice photochemistry are still unclear such as the branching ratios and photo-dissociation cross-sections at different temperatures and irradiation fluxes. This work aims at a quantitative agreement between laboratory experiments and astrochemical modelling of the CH3OH ice UV photolysis. This work also allows us to better understand which processes govern the methanol ice photochemistry present in laboratory experiments. We use ProDiMo to simulate the conditions of laboratory measurements. The simulations start with simple chemistry consisting only of methanol ice and helium to mimic the residual gas in the experimental chamber. A surface chemical network enlarged by photo-dissociation reactions is used to study the chemical reactions within the ice. Additionally, different surface chemistry parameters (surface competition, tunnelling, thermal diffusion and reactive desorption) are adopted to check those that reproduce the experimental results. The chemical models with ProDiMo can reproduce the methanol ice destruction via UV photodissociation at temperatures of 20, 30, 50 and 70 K as observed in the experiments. We note that the results are sensitive to different branching ratios after photolysis and to the mechanisms of reactive desorption. In the simulations of a molecular cloud at 20 K, we observed an increase in the methanol gas abundance of one order of magnitude, with a similar decrease in the solid-phase abundance. Comprehensive astrochemical models provide new insights into laboratory experiments as the quantitative understanding of the processes that govern the reactions within the ice. Ultimately, those insights can help to better interpret astronomical observations.
The laboratory work presented here, simulates the chemistry on icy dust grains as typical for the 'CO freeze-out stage' in dark molecular clouds. It differs from previous studies in that solid-state hydrogenation and vacuum UV-photoprocessing are applied simultaneously to co-depositing molecules. In parallel, the reactions at play are described for fully characterized laboratory conditions. The focus is on the formation of molecules containing both carbon and nitrogen atoms, starting with NO in CO-, H2CO-, and CH3OH-rich ices at 13 K. The experiments yield three important conclusions. 1. Witho…
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
Three structural isomers of the C2H4O2 molecule, namely, methyl formate (MF; HCOOCH3), acetic acid (AA; CH3COOH), and glycol aldehyde (GA; HOCH2CHO), have attracted considerable attention as targets for understanding pathways towards molecular complexity in the interstellar medium (ISM). Among these isomers, MF is decisively abundant in various astronomical objects. For various formation pathways of MF, surface reactions on cosmic dust would play an important role. However, when compared to observations, the formation of MF has been found to be relatively inefficient in laboratory experiments …
The work is devoted to the adaptation of the results of laboratory studies of the laser-induced dissociation of molecules of benzene adsorbed on a quartz substrate to the conditions of the interstellar medium. Adsorption was performed under conditions of low temperature and deep vacuum. The difference between the photolysis of adsorbed molecules and molecules in the gas phase is identified. Significance of process of photolytic desorption in the interstellar conditions is analyzed, in particular, in the conditions of photodissociation regions. It is shown that the efficiency and dissociation c…
The study and quantification of UV photon-induced desorption of frozen molecules furthers our understanding of the chemical evolution of cold interstellar regions. Nitric oxide (NO) is an important intermediate species in both gas-phase and solid-phase chemical networks. In this work, we present quantitative measurements of the photodesorption of a pure NO ice.We used the tunable monochromatic synchrotron light of the DESIRS beamline of the SOLEIL facility near Paris to irradiate NO ices in the 6 - 13.6 eV range and measured desorption by quadrupole mass spectrometry.We find that NO photodesor…
Because chemical reactions on/in cosmic ice dust grains covered by amorphous solid water (ASW) play important roles in generating a variety of molecules, many experimental and theoretical studies have focused on the chemical processes occurring on the ASW surface. In laboratory experiments, conventional spectroscopic and mass-spectrometric detection of stable products is generally employed to deduce reaction channels and mechanisms. However, despite their importance, the details of chemical reactions involving reactive species (i.e., free radicals) have not been clarified because of the absenc…
In dense and cold regions of the interstellar medium (ISM), molecules may be adsorbed onto dust grains to form the ice mantles. Once formed, they can be processed by ionizing radiation coming from stellar or interstellar medium leading to formation of several new molecules in the ice. Among the different kind of ionizing radiation, cosmic rays play an important role in the solid-phase chemistry because of the large amount of energy deposited in the ices. The physicochemical changes induced by the energetic processing of astrophysical ices are recorded in a intrinsic parameter of the matter cal…
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…
Whether ice in cold cosmic environments is physically separated from the silicate dust or mixed with individual silicate moieties is not known. However, different grain models give very different compositions and temperatures of grains. The aim of the present study is a comparison of the mid-IR spectra of laboratory silicate-grains/water-ice mixtures with astronomical observations to evaluate the presence of dust/ice mixtures in interstellar and circumstellar environments. The laboratory data can explain the observations assuming reasonable mass-averaged temperatures for the protostellar envel…
CO$_2$ ice is an important reservoir of carbon and oxygen in star and planet forming regions. Together with water and CO, CO$_2$ sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO$_2$ ice spectroscopy is a prerequisite to characterize CO$_2$ interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO$_2$ longitudinal optical (LO) phonon mode in pure CO$_2$ ice and i…
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）
The hunt for formamide in interstellar ices: A toolkit of laboratory infrared spectra in astronomically relevant ice mixtures and comparisons to ISO, Spitzer, and JWST observations
Hydroxylamine (NH2OH) is one of the potential precursors of complex pre-biotic species in space. Here we present a detailed experimental study of hydroxylamine formation through nitric oxide (NO) surface hydrogenation for astronomically relevant conditions. The aim of this work is to investigate hydroxylamine formation efficiencies in polar (water-rich) and non-polar (carbon monoxide-rich) interstellar ice analogues. A complex reaction network involving both final (N2O, NH2OH) and intermediate (HNO, NH2O, etc.) products is discussed. The main conclusion is that hydroxylamine formation takes pl…
Broad infrared emission features (e.g., at 3.3, 6.2, 7.7, 8.6, and 11.3 microns) from the gas phase interstellar medium have long been attributed to polycyclic aromatic hydrocarbons (PAHs). A significant portion (10%-20%) of the Milky Way's carbon reservoir is locked in PAH molecules, which makes their characterization integral to our understanding of astrochemistry. In molecular clouds and the dense envelopes and disks of young stellar objects (YSOs), PAHs are expected to be frozen in the icy mantles of dust grains where they should reveal themselves through infrared absorption. To facilitate…
Ice desorption affects the evolution of the gas-phase chemistry during the protostellar stage, and also determines the chemical composition of comets forming in circumstellar disks. From observations, most volatile species are found in H2O-dominated ices. The aim of this study is first to experimentally determine how entrapment of volatiles in H2O ice depends on ice thickness, mixture ratio and heating rate, and second, to introduce an extended three-phase model (gas, ice surface and ice mantle) to describe ice mixture desorption with a minimum number of free parameters. Thermal H2O:CO2 ice de…
Context. The gas and ice-grain chemistry of the pre-stellar core L1544 has been the subject of several observations and modelling studies conducted in the past years. The chemical composition of the ice mantles reflects the environmental physical changes along the temporal evolution. The investigation outcome hints at a layered structure of interstellar ices with mainly H$_2$O in the inner layers and an increasing amount of CO near the surface. The morphology of interstellar ice analogues can be investigated experimentally. Aims. This research presents a new approach of a three-dimensional fit…
Context. A variety of laboratory ice spectra simulating different chemical environments, ice morphology as well as thermal and energetic processing are demanded to provide an accurate interpretation of the infrared spectra of protostars. To answer which combination of laboratory data best fit the observations, an automated statistically-based computational approach becomes necessary. Aims. To introduce a new approach, based on evolutionary algorithms, to search for molecules in ice mantles via spectral decomposition of infrared observational data with laboratory ice spectra. Methods. A publicl…
Two different silicate/water ice mixtures representing laboratory analogues of interstellar and circumstellar icy grains were produced in the laboratory. For the first time, optical constants, the real and imaginary parts of the complex refractive index, of such silicate/water ice mixtures were experimentally determined in the mid-infrared spectral region at low temperatures. In addition, optical constants of pure water ice and pure silicates were derived in the laboratory. Two sets of constants were compared, namely, measured constants calculated from the transmission spectra of silicate/wate…
Solid state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH3 and HNCO, and prebiotic molecules, specifically amino acids. To date, the chemical origin of such small nitrogen containing species is still not well understood, despite the fact that ammonia is an abundant constituent of interstellar ices toward young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of the present work is to experimentally investigate the formation routes of NH3 and HNCO thro…
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…
The catalytic role of dust grain surfaces in the thermal reaction CO2 + 2NH3 $\rightarrow$ NH4+NH2COO was recently demonstrated by our group. The rate coefficients for the reaction at 80 K on the surface of nanometre-sized carbon and silicate grains were measured to be up to three times higher compared to the reaction rate coefficients measured on KBr. In this study, the reaction was performed on carbon grains and on KBr in the extended temperature range of 50 - 80 K and with the addition of water ice. The reaction activation energy was found to be about 3 times lower on grains compared to the…
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））
Understanding the history and evolution of small bodies, such as dust grains and comets, in planet-forming disks is very important to reveal the architectural laws responsible for the creation of planetary systems. These small bodies in cold regions of the disks are typically considered as mixtures of dust particles with molecular ices, where ices cover the surface of a dust core or are actually physically mixed with dust. Whilst the first case, ice-on-dust, has been intensively studied in the laboratory in recent decades, the second case, ice-mixed-with-dust, present uncharted territory. This…
Water (H2O) ice is ubiquitous component of the universe, having been detected in a variety of interstellar and Solar System environments where radiation plays an important role in its physico-chemical transformations. Although the radiation chemistry of H2O astrophysical ice analogues has been well studied, direct and systematic comparisons of different solid phases are scarce and are typically limited to just two phases. In this article, we describe the results of an in-depth study of the 2 keV electron irradiation of amorphous solid water (ASW), restrained amorphous ice (RAI) and the cubic (…
1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subseq…
A prevailing theory for the interstellar production of complex organic molecules (COMs) involves formation on warm dust-grain surfaces, via the diffusion and reaction of radicals produced through grain-surface photodissociation of stable molecules. However, some gas-phase O-bearing COMs, notably acetaldehyde(CH$_3$CHO), methyl formate(CH$_3$OCHO), and dimethyl ether(CH$_3$OCH$_3$), are now observed at very low temperatures, challenging the warm scenario. Here, we introduce a selection of new non-diffusive mechanisms into an astrochemical model, to account for the failure of the standard diffus…
Complex organic molecules (COMs) have been observed in comets, hot cores and cold dense regions of the interstellar medium. It is generally accepted that these COMs form on icy dust grain through the recombination reaction of radicals triggered by either energetic UV- photon or non-energetic H-atom addition processing. In this work, we present for the first time laboratory studies that allow for quantitative comparison of hydrogenation and UV-induced reactions as well as their cumulative effect in astronomically relevant CO:CH3OH=4:1 ice analogues. The formation of glycolaldehyde (GA) and ethy…
Hot corino chemistry and warm carbon chain chemistry (WCCC) are driven by gas-grain interactions in star-forming cores: radical-radical recombination reactions to form complex organic molecules (COMs) in the ice mantle, sublimation of CH$_4$ and COMs, and their subsequent gas-phase reactions. These chemical features are expected to depend on the composition of ice mantle which is set in the prestellar phase. We calculated the gas-grain chemical reaction network considering a layered ice-mantle structure in star-forming cores, to investigate how the hot corino chemistry and WCCC depend on the p…
Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, i.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic ray induced UV-photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently form…
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）
A fast machine learning tool to predict the composition of astronomical ices from infrared absorption spectra
Centro de Astrobiología (CAB), CSIC-INTA（天体生物学中心）；Facultad de Ciencias Físicas, Universidad Complutense de Madrid（马德里康普顿斯大学物理科学学院）；LIRA, CY Cergy Paris Université（CY塞吉巴黎大学 LIRA 实验室）；Instituto de Estructura de la Materia (IEM), CSIC（物质结构研究所）；MasOrange；Laboratory for Astrophysics, Leiden Observatory, Leiden University（莱顿大学莱顿天文台天体物理实验室）
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 activation energy for desorption (Edes) and that for surface diffusion (Esd) of adsorbed molecules on dust grains are two of the most important parameters for the chemistry in the interstellar medium. Although Edes is often measured by laboratory experiments, the measurement of Esd is sparse. Due to the lack of data, astrochemical models usually assume a simple scaling relation, Esd = fEdes, where f is a constant, irrespective of adsorbed species. Here, we experimentally measure Esd for CH4, H2S, OCS, CH3OH, and CH3CN on water-ice surfaces using an ultra-high-vacuum transmission electron m…
The Ice Chamber for Astrophysics-Astrochemistry (ICA) is a new laboratory end-station located at the Institute for Nuclear Research (Atomki) in Debrecen, Hungary. The ICA has been specifically designed for the study of the physico-chemical properties of astrophysical ice analogues and their chemical evolution when subjected to ionising radiation and thermal processing. The ICA is an ultra-high vacuum compatible chamber containing a series of IR-transparent substrates mounted in a copper holder connected to a closed-cycle cryostat capable of being cooled down to 20 K, itself mounted on a 360° r…
