Context. Evaporative (sublimation) cooling of icy interstellar grains occurs when the grains have been suddenly heated by a cosmic-ray (CR) particle or other process. It results in thermal desorption of icy species, affecting the chemical composition of interstellar clouds. Aims. We investigate details on sublimation cooling, obtaining necessary knowledge before this process is considered in astrochemical models. Methods. We employed a numerical code that describes the sublimation of molecules from an icy grain, layer by layer, also considering a limited diffusion of bulk-ice molecules toward the surface before they sublimate. We studied a grain, suddenly heated to peak temperature T, which cools via sublimation and radiation. Results. A number of questions were answered. The choice of grain heat capacity C has a limited effect on the number of sublimated molecules N, if the grain temperature T > 40K. For grains with different sizes, CR-induced desorption is most efficient for rather small grains with a core radius of a ~ 0.02 micron. CR-induced sublimation of CO2 ice can occur only from small grains if their peak temperature is T > 80K and there is a lack of other volatiles. The presence of H2 molecules on grain surface hastens their cooling and thus significantly reduces N for other sublimated molecules for T < 30K. Finally, if there is no diffusion and subsequent sublimation of bulk-ice molecules (i.e., sublimation occurs only from the surface layer), sublimation yields do not exceed 1-2 monolayers and, if T > 50K, N does not increase with increasing T. Conclusions. Important details regarding the sublimation cooling of icy interstellar grains were clarified, which will enable a proper consideration of this process in astrochemical modeling.
Context. While radiative cooling of interstellar grains is a well-known process, little detail is known about the cooling of grains with an icy mantle that contains volatile adsorbed molecules. Aims. We explore basic details for the cooling process of an icy grain with properties relevant to dark interstellar clouds. Methods. Grain cooling was described with a numerical code considering a grain with an icy mantle that is structured in monolayers and containing several volatile species in proportions consistent with interstellar ice. Evaporation was treated as first-order decay. Diffusion and s…
Observations of gaseous complex organic molecules (COMs) in cold starless and prestellar cloud cores require efficient desorption of the COMs and their parent species from icy mantles on interstellar grains. With a simple astrochemical model, we investigate if mechanical removal of ice fragments in oblique collisions between grains in two size bins (0.01 and 0.1 micron) can substantially affect COM abundances. Two grain collision velocities were considered - 10 and 50 meters per second, corresponding to realistic grain relative speeds arising from ambipolar diffusion and turbulence, respective…
We study the destruction and modification of icy interstellar objects by cosmic rays and gas collisions. Using the cosmic-ray flux measured in the local interstellar medium as well as inferred from gamma-ray observations at the different galactocentric radii, we find that cosmic-ray erosion is significant for interstellar objects made of common types of ices. Interestingly, cosmic-ray heating might destroy icy interstellar objects very efficiently such that the initial size of an N$_2$ fragment as suggested by \citet{jackson2021} to explain the composition of `Oumuamua should be at least 0.5 k…
Interstellar grains are known to be important actors in the formation of interstellar molecules such as H$_2$, water, ammonia, and methanol. It has been suggested that the so-called interstellar complex organic molecules (iCOMs) are also formed on the interstellar grain icy surfaces by the combination of radicals via reactions assumed to have an efficiency equal to unity. In this work, we aim to investigate the robustness or weakness of this assumption by considering the case of acetaldehyde (CH$_3$CHO) as a starting study case. In the literature, it has been postulated that acetaldehyde is fo…
The binding energies (BE) of molecules on the interstellar grains are crucial in the chemical evolution of the interstellar medium (ISM). Both temperature programmed desorption (TPD) laboratory experiments and quantum chemistry computations have often provided, so far, only single values of the BE for each molecule. This is a severe limitation, as the ices enveloping the grain mantles are structurally amorphous, giving rise to a manifold of possible adsorption sites, each with different BEs. However, the ice amorphous nature prevents the knowledge of structural details, hindering the developme…
Processing by interstellar photons affects the composition of the icy mantles on interstellar grains. The rate of photodissociation in solids differs from that of molecules in the gas phase. The aim of this work was to determine an average, general ratio between photodissociation coefficients for molecules in ice and gas. A 1D astrochemical model was utilized to simulate the chemical composition for a line of sight through a collapsing interstellar cloud core, whose interstellar extinction changes with time. At different extinctions, the calculated column densities of icy carbon oxides and amm…
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…
Data from the Five College Radio Astronomy Observatory CO Mapping Survey of the Taurus molecular cloud are combined with extinction data for a sample of 292 background field stars to investigate the uptake of CO from the gas to icy grain mantles on dust within the cloud. On the assumption that the reservoir of CO in the ices is well represented by the combined abundances of solid CO and solid CO2 (which forms by oxidation of CO on the dust), we find that the total column density (gas + solid) correlates tightly with visual extinction (Av) over the range 5 < Av < 30 mag, i.e., up to the highest…
Quantum chemical cluster calculations show that reactions of C$^+$ with HCN or HNC embedded in the surface of an icy grain mantle can account for the formation of a recently detected molecule, glycolonitrile, which is considered to be an important precursor to ribonucleic compounds. Reactions of cations deposited on ice mantles with minimal kinetic energy have been found theoretically to result in previously unknown pathways to significant organic compounds in protostellar systems and the interstellar medium. In density functional theory cluster calculations involving up to 24H$_2$O, C$^+$ rea…
Analyses of infrared signatures of CO$_2$ in water dominated ices in the ISM can give information on the physical state of CO$_2$ in icy grains and on the thermal history of the ices themselves. In many sources, CO$_2$ was found in the `pure' crystalline form, as signatured by the splitting in the bending mode absorption profile. To a large extent, pure CO$_2$ is likely to have formed from segregation of CO$_2$ from a CO$_2$:H$_2$O mixture during thermal processing. Previous laboratory studies quantified the temperature dependence of segregation, but no systematic measurement of the concentrat…
The role of the pre-exponential factor on temperature programmed desorption spectra: A computational study of frozen species on interstellar icy grain mantles
The first interstellar object observed in our solar system, 1I/2017 U1 (`Oumuamua), exhibited a number of peculiar properties, including extreme elongation and acceleration excess. Recently, \cite{Seligman:2020vb} proposed that the object was made out of molecular hydrogen (H$_{2}$) ice. The question is whether H$_2$ objects could survive their travel from the birth sites to the solar system. Here we study destruction processes of icy H$_2$ objects through their journey from giant molecular clouds (GMCs) to the interstellar medium (ISM) and the solar system, owing to interstellar radiation, ga…
Icy grains in the interstellar medium and star-formation regions consist of a variety of materials. Such composite grains interact differently with cosmic-ray (CR) particles compared to simple single-material grains. We aim to calculate the spectra of energies and temperatures of mixed-composition grains undergoing whole-grain heating by CRs. The grains were assumed to consist of a mixture of carbon and olivine, covered by ices consisting of carbon oxides and water. The energy and temperature spectra for grains with radii 0.05; 0.1, and 0.2 microns impacted by CRs were calculated for eight val…
Formamide has a key role in prebiotic chemistry as it is the simplest molecule containing the four most important atoms from a biological point of view: hydrogen, carbon, nitrogen and oxygen. Due to its importance, the formation of this molecule has been studied and different pathways have been considered both in gas-phase and on ices of dust grains since it was first detected. In the present work, the thermodynamics of the formation route of formamide starting from NH2 and H2CO, a reaction channel proposed to occur in the gas phase, has been theoretically investigated in the scenario taking p…
Dust Activity Evolution and Constraints on Icy Grains in the Interstellar Comet 3I/ATLAS
State Key Laboratory of Lunar and Planetary Sciences, Macau University of Science and Technology（澳门科技大学月球与行星科学国家重点实验室）；School of Aeronautics and Astronautics, Shenzhen Campus of Sun Yat-sen University（中山大学深圳校区航空航天学院）；Shanghai Astronomical Observatory, Chinese Academy of Sciences（中国科学院上海天文台）
The problem of impulsive heating of dust grains in cold, dense interstellar clouds is revisited theoretically, with the aim to better understand leading mechanisms of the explosive desorption of icy mantles. It is rigorously shown that if the heating of a reactive medium occurs within a sufficiently localized spot (e.g., heating of mantles by cosmic rays), then the subsequent thermal evolution is characterized by a single dimensionless number $λ$. This number identifies a bifurcation between two distinct regimes: When $λ$ exceeds a critical value (threshold), the heat equation exhibits the exp…
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…
Formation of interstellar complex organic molecules is currently thought to be dominated by the barrierless coupling between radicals on the interstellar icy grain surfaces. Previous standard DFT results on the reactivity between CH$_3$ and HCO on amorphous water surfaces, showed that formation of CH$_4$ + CO by H transfer from HCO to CH$_3$ assisted by water molecules of the ice was the dominant channel. However, the adopted description of the electronic structure of the biradical (i.e., CH$_3$/HCO) system was inadequate (without the broken-symmetry (BS) approach). In this work, we revisit th…
The icy mantles of interstellar dust grains are the birthplaces of the primordial prebiotic molecular inventory that may eventually seed nascent solar systems and the planets and planetesimals that form therein. Here, we present a study of two of the most abundant species in these ices after water: carbon dioxide (CO2) and methanol (CH3OH) using TeraHertz (THz) time-domain spectroscopy and mid-infrared spectroscopy. We study pure and mixed-ices of these species, and demonstrate the power of the THz region of the spectrum to elucidate the long-range structure (i.e. crystalline versus amorphous)…
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…
Interstellar complex organic molecules (iCOMs) can be loosely defined as chemical compounds with at least six atoms in which at least one is carbon. The observations of iCOMs in star-forming regions have shown that they contain an important fraction of carbon in a molecular form, which can be used to synthesize more complex, even biotic molecules. Hence, iCOMs are major actors in the increasing molecular complexity in space and they might have played a role in the origin of terrestrial life. Understand-ing how iCOMs are formed is relevant for predicting the ultimate organic chemistry reached i…
Freeze-out of the gas phase elements onto cold grains in dense interstellar and circumstellar media builds up ice mantles consisting of molecules that are mostly formed in situ (H2O, NH3, CO2, CO, CH3OH, and more). This review summarizes the detected infrared spectroscopic ice features and compares the abundances across Galactic, extragalactic, and solar system environments. A tremendous amount of information is contained in the ice band profiles. Laboratory experiments play a critical role in the analysis of the observations. Strong evidence is found for distinct ice formation stages, separat…
Interstellar molecules are thought to build up in the shielded environment of molecular clouds or in the envelope of evolved stars. This follows many sequential reaction steps of atoms and simple molecules in the gas phase and/or on (icy) grain surfaces. However, these chemical routes are highly inefficient for larger species in the tenuous environment of space as many steps are involved and, indeed, models fail to explain the observed high abundances. This is definitely the case for the C$_{60}$ fullerene, recently identified as one of the most complex molecules in the interstellar medium. Ob…
Cosmic rays are able to heat interstellar dust grains. This may enhance molecule mobility in icy mantles that have accumulated on the grains in dark cloud cores. A three-phase astrochemical model was used to investigate the molecule mobility in interstellar ices. Specifically, diffusion through pores in ice between the subsurface mantle and outer surface, assisted by whole-grain heating, was considered. It was found that the pores can serve as an efficient transport route for light species. The diffusion of chemical radicals from the mantle to the outer surface are most effective. These specie…
For the first time, we report a unified microscopic-macroscopic Monte Carlo simulation of gas-grain chemistry in cold interstellar clouds in which both the gas-phase and the grain surface chemistry are simulated by a stochastic technique. The surface chemistry is simulated with a microscopic Monte Carlo method in which the chemistry occurs on an initially flat surface. The surface chemical network consists of 29 reactions initiated by the accreting species H, O, C, and CO. Four different models are run with diverse but homogeneous physical conditions including temperature, gas density, and dif…
In this work we investigate the effects of ion accretion and size-dependent dust temperatures on the abundances of both gas-phase and grain-surface species. While past work has assumed a constant areal density for icy species, we show that this assumption is invalid and the chemical differentiation over grain sizes are significant. We use a gas-grain chemical code to numerically demonstrate this in two typical interstellar conditions: dark cloud (DC) and cold neutral medium (CNM). It is shown that, although the grain size distribution variation (but with the total grain surface area unchanged)…
Notwithstanding manufacture of complex organic molecules from impacting cometary and icy planet surface analogues is well-established, dust grain-grain collisions driven by turbulence in interstellar or circumstellar regions may represent a parallel chemical route toward the shock synthesis of prebiotically relevant species. Here we report on a study, based on the multi-scale shock-compression technique combined with ab initio molecular dynamics approaches, where the shock-waves-driven chemistry of mutually colliding isocyanic acid (HNCO) containing icy grains has been simulated by first-princ…
Ethanol (CH$_3$CH$_2$OH) is a relatively common molecule, often found in star forming regions. Recent studies suggest that it could be a parent molecule of several so-called interstellar complex organic molecules (iCOMs). Yet, the formation route of this species remains debated. In the present work, we study the formation of ethanol through the reaction of CCH with one H$_2$O molecule belonging to the ice, as a test case to investigate the viability of chemical reactions based on a "radical + ice component" scheme as an alternative mechanism for the synthesis of iCOMs, beyond the usual radical…
Cyanamide (NH2CN) and its isomer, carbodiimide (HNCNH), may form adenine in the interstellar medium (ISM) via a series of reactions. Therefore, they are considered key prebiotic molecules in the study of the origin of life. We used the three-phase NAUTILUS chemical code, which includes the gas, the dust surface, and the icy mantle, to investigate the formation and destruction of cyanamide and carbodiimide. We added over 200 new chemical reactions of the two isomers and related species, and established a relatively complete network. We applied cold core, hot corino/core and shock models to simu…
We present the first detection of gas phase S2H in the Horsehead, a moderately UV-irradiated nebula. This confirms the presence of doubly sulfuretted species in the interstellar medium and opens a new challenge for sulfur chemistry. The observed S2H abundance is ~5x10$^{-11}$, only a factor 4-6 lower than that of the widespread H2S molecule. H2S and S2H are efficiently formed on the UV-irradiated icy grain mantles. We performed ice irradiation experiments to determine the H2S and S2H photodesorption yields. The obtained values are ~1.2x10$^{-3}$ and <1x10$^{-5}$ molecules per incident photon f…
Discovery of thionylimide, HNSO, in space: the first N-, S- and O-bearing interstellar molecule
Centro de Astrobiología (CAB), INTA-CSIC（天体生物学中心）；I. Physikalisches Institut, Universität zu Köln（科隆大学第一物理研究所）；Star and Planet Formation Laboratory, Cluster for Pioneering Research, RIKEN（理化学研究所前沿研究集群星与行星形成实验室）
Context. The abundances of many observed compounds in interstellar molecular clouds still lack an explanation, despite extensive research that includes both gas and solid (dust-grain surface) phase reactions. Aims. We aim to qualitatively prove the idea that a hydrogen-poor subsurface chemistry on interstellar grains is responsible for at least some of these chemical "anomalies". This chemistry develops in the icy mantles when photodissociation reactions in the mantle release free hydrogen, which escapes the mantle via diffusion. This results in serious alterations of the chemical composition …
Cosmic-ray-induced whole-grain heating induces evaporation and other processes that affect the chemistry of interstellar clouds. With recent data on grain heating frequencies as an input for a modified rate-equation astrochemical model, this study examines, which whole-grain heating temperature regime is the most efficient at altering the chemical composition of gas and ices. Such a question arises because low-temperature heating, albeit less effective at inducing evaporation of adsorbed species, happens much more often than high-temperature grain heating. The model considers a delayed gravita…
JWST Observations of Young protoStars (JOYS+): Detection of icy complex organic molecules and ions. I. CH$_4$, SO$_2$, HCOO$^-$, OCN$^-$, H$_2$CO, HCOOH, CH$_3$CH$_2$OH, CH$_3$CHO, CH$_3$OCHO, CH$_3$COOH
Molecular hydrogen is the most abundant molecular species in the Universe. While no doubts exist that it is mainly formed on the interstellar dust grain surfaces, many details of this process remain poorly known. In this work, we focus on the fate of the energy released by the H$_2$ formation on the dust icy mantles, how it is partitioned between the substrate and the newly formed H$_2$, a process that has a profound impact on the interstellar medium. We carried out state-of-art \textit{ab-initio} molecular dynamics simulations of H$_2$ formation on periodic crystalline and amorphous ice surfa…
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…
Stellar systems are often formed through the collapse of dense molecular clouds which, in turn, return copious amounts of atomic and molecular material to the interstellar medium. An in-depth understanding of chemical evolution during this cyclic interaction between the stars and the interstellar medium is at the heart of astrochemistry. Systematic chemical composition changes as interstellar clouds evolve from the diffuse stage to dense, quiescent molecular clouds to star-forming regions and proto-planetary disks further enrich the molecular diversity leading to the evolution of ever more com…
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…
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…
The evolution of star-forming regions and their thermal balance are strongly influenced by their chemical composition, that, in turn, is determined by the physico-chemical processes that govern the transition between the gas phase and the solid state, specifically icy dust grains (e.g., particles adsorption and desorption). Gas-grain and grain-gas transitions as well as formation and sublimation of interstellar ices are thus essential elements of understanding astrophysical observations of cold environments (e.g., pre-stellar cores) where unexpected amounts of a large variety of chemical speci…
Interstellar ice grains are believed to play a key role in the formation of many of the simple and complex organic species detected in space. However, many fundamental questions on the physicochemical processes linked to the formation and survival of species in ice grains remain unanswered. Field work at large-scale facilities such as free-electron lasers (FELs) can aid the investigation of the composition and morphology of ice grains by providing novel tools to the laboratory astrophysics community. We combined the high tunability, wide infrared spectral range and intensity of the FEL beam li…
JWST Reveals Refractory-Rich Water Ice in Interstellar Comet 3I/ATLAS: Evidence for a Continuum of Grain Properties across Protoplanetary Disks
Southwest Research Institute（西南研究院）；University of Maryland, College Park（马里兰大学帕克分校）；NASA Goddard Space Flight Center（美国宇航局戈达德太空飞行中心）；Catholic University of America（美利坚天主教大学）；Auburn University（奥本大学）；Universität Bern（伯尔尼大学）
Icy grain mantles are the main reservoir of the volatile elements that link chemical processes in dark, interstellar clouds with the formation of planets and composition of their atmospheres. The initial ice composition is set in the cold, dense parts of molecular clouds, prior to the onset of star formation. With the exquisite sensitivity of JWST, this critical stage of ice evolution is now accessible for detailed study. Here we show the first results of the Early Release Science program "Ice Age" that reveal the rich composition of these dense cloud ices. Weak ices, including, $^{13}$CO$_2$,…
This work aims to constrain the abundances of interstellar amides, by searching for this group of prebiotic molecules in the intermediate-mass protostar Serpens SMM1-a. ALMA observations are conducted toward Serpens SMM1. A spectrum is extracted toward the SMM1-a position and analyzed with the CASSIS line analysis software for the presence of characteristic rotational lines of a number of amides and other molecules. NH$_{2}$CHO, NH$_{2}$CHO $ν_{12}$=1, NH$_{2}^{13}$CHO, CH$_{3}$C(O)NH$_{2}$ $ν$=0,1, CH$_{2}$DOH, CH$_{3}$CHO, and CH$_{3}$C(O)CH$_{3}$ are securely detected, while trans-NHDCHO, N…
