One of the major obstacles to accurately model the interstellar chemistry is an inadequate knowledge about the binding energy (BE) of interstellar species with dust grains. In denser region of molecular cloud, where very complex chemistry is active, interstellar dust is predominantly covered by H2O molecules and thus it is essential to know the interaction of gas phase species with water ice to trace realistic physical and chemical processes. To this effect, we consider water (cluster) ice to calculate the BE of several atoms, molecules, and radicals of astrochemical interest. Systematic studies have been carried out to come up with a relatively more accurate BE of astrophysically relevant species on water ice. We increase the size of the water cluster methodically to capture the realistic situation. Sequentially one, three, four, five and six water molecules are considered to represent water ice analogue in increasing order of complexity. We notice that for most of the species considered here, as we increase the cluster size, our calculated BE value starts to converge towards the experimentally obtained value. More specifically, our computed results with water c-pentamer (average deviation from experiment ~ 15.8%) and c-hexamer (chair) (average deviation from experiment ~ 16.7%) configuration are found to be more nearer as the experimentally obtained value than other water clusters considered.
Despite low elemental abundance of atomic deuterium in interstellar medium (ISM), observational evidences suggest that several species in gas-phase and in ices could be heavily fractionated. We explore various aspects of deuterium enrichment by constructing a chemical evolution model in gas and grain phases. Depending on various physical parameters, gas and grains are allowed to interact with each other through exchange of their chemical species. It is known that HCO+ and N2H+ are two abundant gas phase ions in ISM and their deuterium fractionation are generally used to predict degree of ioniz…
A good understanding of the ionization rates of neutral species in the heliosphere is important for studies of the heliosphere and planetary atmospheres. So far, the intensities of the ionization reactions have been studied based on observations of the contributing phenomena, such as the solar spectral flux in the EUV band and the flux of the solar wind protons, alpha particles, and electrons. The results strongly depend on absolute calibration of these measurements, which, especially for the EUV measurements, is challenging. Here, we propose a novel method of determining the ionization rate o…
With the well-established correlation between the relative stabilities of isomers and their interstellar abundances coupled with the prevalence of isomeric species among the interstellar molecular species, isomerization remains a plausible formation route for isomers in the interstellar medium. The present work reports an extensive investigation of the isomerization energies of 246 molecular species from 65 isomeric groups using the Gaussian-4 theory composite method with atoms ranging from 3 to 12. From the results, the high abundances of the most stable isomers coupled with the energy source…
Phosphorus related species are not known to be as omnipresent in space as hydrogen, carbon, nitrogen, oxygen, and sulfur-bearing species. Astronomers spotted very few P-bearing molecules in the interstellar medium and circumstellar envelopes. Limited discovery of the P-bearing species imposes severe constraints in modeling the P-chemistry. In this paper, we carry out extensive chemical models to follow the fate of P-bearing species in diffuse clouds, photon-dominated or photodissociation regions (PDRs), and hot cores/corinos. We notice a curious correlation between the abundances of PO and PN …
The knowledge of the binding energy of molecules on astrophysically relevant ices can help to obtain an estimate of the desorption rate, i.e. the molecules residence time on the surface. This represents an important parameter for astrochemical models, crucial to determine the chemical fate of complex organic molecules formed on dust grains and observed in the densest regions of the interstellar medium. In this work, we propose a new robust procedure to study the interaction of atoms and molecules with interstellar ices, based on \textit{ab initio} molecular dynamics and density functional theo…
Straight-chain (normal-propyl cyanide, n - C3H7CN) and branched-chain (iso-propyl cyanide, i - C3H7CN) alkyl cyanides are recently identified in the massive star-forming regions (Sgr B2(N) and Orion). These branched-chain molecules indicate that the key amino acids (side-chain structures) may also be present in a similar region. The process by which this branching could propagate towards the higher-order (butyl cyanide, C4H9CN) is an active field of research. Since the grain catalysis process could have formed a major portion of these species, considering a realistic set of binding energies ar…
We report the first interstellar detection of c-C3D2. The doubly deuterated cyclopropenylidene, a carbene, has been detected toward the starless cores TMC- 1C and L1544 using the IRAM 30m telescope. The J(Ka,Kc) = 3(0,3)-2(1,2), 3(1,3)-2(0,2), and 2(2,1)-1(1,0) transitions of this species have been observed at 3 mm in both sources. The expected 1:2 intensity ratio has been found in the 3(0,3)-2(1,2) and 3(1,3)-2(0,2) lines, belonging to the para and ortho species respectively. We also observed lines of the main species, c-C3H2, the singly deuterated c-C3HD, and the species with one 13C off of …
The abundance of interstellar ice constituents is usually expressed with respect to the water ice because, in denser regions, a significant portion of the interstellar grain surface would be covered by water ice. The binding energy (BE), or adsorption energy of the interstellar species regulates the chemical complexity of the interstellar grain mantle. Due to the high abundance of water ice, the BE of surface species with the water is usually provided and widely used in astrochemical modeling. However, the hydrogen molecules would cover some part of the grain mantle in the denser and colder pa…
A basic model for the formation of non-equilibrium rotational energy distributions is described for reactive, homo-polar diatomic molecules and ions in the interstellar medium. Kinetic models were constructed to calculate the rotational populations of C2+ under the conditions it would experience in the diffuse interstellar medium. As the non-polar ion reacts with molecular hydrogen, but not atomic hydrogen, the thermalization of a hot nascent rotational population will be arrested by chemical reaction when the H2 density begins to be significant. Populations that deviate strongly from the loca…
Advanced telescopes, such as ALMA and JWST, are likely to show that the chemical universe may be even more complex than currently observed, requiring astrochemical modelers to improve their models to account for the impact of new data. However, essential input information for gas-grain models, such as binding energies of molecules to the surface, have been derived experimentally only for a handful of species, leaving hundreds of species with highly uncertain estimates. We present in this paper a systematic study of the effect of uncertainties in the binding energies on an astrochemical two-pha…
Context. The presence of dust in the interstellar medium has profound consequences on the chemical composition of regions where stars are forming. Recent observations show that many species formed onto dust are populating the gas phase, especially in cold environments where UV and CR induced photons do not account for such processes. Aims. The aim of this paper is to understand and quantify the process that releases solid species into the gas phase, the so-called chemical desorption process, so that an explicit formula can be derived that can be included into astrochemical models. Methods. We …
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)…
The distribution of molecules between the gas and solid phase during star and planet formation, determines the trajectory of gas and grain surface chemistry, as well as the delivery of elements to nascent planets. This distribution is primarily set by the binding energies of different molecules to water ice surfaces. We computationally estimated the binding energies of ten astrochemically relevant P-bearing species on water surface, we also validate our method for 20 species with known binding energies. We used DFT calculations (M06-2X/aug-cc-pVDZ) to calculate the energetics of molecules and …
Context. Interstellar dust particles, which represent 1% of the total mass, are recognized to be very powerful interstellar catalysts in star-forming regions. The presence of dust can have a strong impact on the chemical composition of molecular clouds. While observations show that many species that formed onto dust grains populate the gas phase, the process that transforms solid state into gas phase remains unclear. Aims. The aim of this paper is to consider the chemical desorption process, i.e. the process that releases solid species into the gas phase, in astrochemical models. These models …
Main focus of this paper is to explore the possibility of findings two deuterated isotopomers of H2Cl+ (Chloronium) in and around the Interstellar Medium (ISM). Presence of Chloronium ion has recently been confirmed by Herschel Space Observatory's Heterodyne Instrument for the Far-Infrared (Neufeld et al., 2012). It observed para-chloronium towards six sources in the Galaxy. Existence of its deuterated isotopomers (HDCl+ & D2Cl+) are till date not discussed in the literature. We find that these deuterated gas phase ions could be destroyed by various ion-molecular reactions, dissociative recomb…
$H_2$ is the most abundant interstellar species. Its deuterated forms ($HD$ and $D_2$) are also significantly abundant. Huge abundances of these molecules could be explained by considering the chemistry occurring on the interstellar dust. Because of its simplicity, Rate equation method is widely used to study the formation of grain-surface species. However, since recombination efficiency of formation of any surface species are heavily dependent on various physical and chemical parameters, Monte Carlo method would be best method suited to take care of randomness of the processes. We perform Mon…
We discuss the absorption due to various constituents of the interstellar medium of M82 seen in moderately high resolution, high signal-to-noise ratio optical spectra of SN 2014J. Complex absorption from M82 is seen, at velocities 45 $\le$ $v_{\rm LSR}$ $\le$ 260 km s$^{-1}$, for Na I, K I, Ca I, Ca II, CH, CH$^+$, and CN; many of the diffuse interstellar bands (DIBs) are also detected. Comparisons of the column densities of the atomic and molecular species and the equivalent widths of the DIBs reveal both similarities and differences in relative abundances, compared to trends seen in the ISM …
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…
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…
We have revisited the chemistry of chlorine-bearing species in the diffuse interstellar medium with new observations of the HCl$^+$ molecular ion and new astrochemical models. Using the GREAT instrument on board SOFIA, we observed the $^2Π_{3/2}\, J = 5/2 - 3/2$ transition of HCl$^+$ near 1444 GHz toward the bright THz continuum source W49N. We detected absorption by diffuse foreground gas unassociated with the background source, and were able to thereby measure the distribution of HCl$^+$ along the sight-line. We interpreted the observational data using an updated version of an astrochemical …
Context: Diffusion of species on the dust surface is a key process for determining the chemical composition of interstellar ices. On the dust surface, adsorbed species diffuse from one potential well to another and react with other adsorbed reactants, resulting in the formation of simple and complex molecules. Aims: We study the impact on the abundances of the species simulated by the chemical codes by considering the uncertainties in the diffusion energy of adsorbed species. We aim to limit the uncertainties in the abundances as calculated by chemical codes by identifying the surface species …
In the denser and colder ($\leq$20 K) regions of the interstellar medium (ISM), near-infrared observations have revealed the presence of sub-micron sized dust grains covered by several layers of H\textsubscript{2}O-dominated ices and dirtied by the presence of other volatile species. Whether a molecule is in the gas or solid-phase depends on its binding energy (BE) on ice surfaces. Thus, BEs are crucial parameters for the astrochemical models that aim to reproduce the observed evolution of the ISM chemistry. In general, BEs can be inferred either from experimental techniques or by theoretical …
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…
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…
Theoretical studies have revealed that dust grains are usually moving fast through the turbulent interstellar gas, which could have significant effects upon interstellar chemistry by modifying grain accretion. This effect is investigated in this work on the basis of numerical gas-grain chemical modeling. Major features of the grain motion effect in the typical environment of dark clouds (DC) can be summarised as follows: 1) decrease of gas-phase (both neutral and ionic) abundances and increase of surface abundances by up to 2-3 orders of magnitude; 2) shifts of the existing chemical jumps to e…
Phosphorus-bearing species are an essential key to form life on Earth, however they have barely been detected in the interstellar medium. Since only PN and PO have been identified so far towards star-forming regions, the chemical formation pathways of P-bearing molecules are not easy to constrain and are thus highly debatable. An important factor still missing in the chemical models is the initial elemental abundance of phosphorus, i.e. the depletion level of P. In order to overcome this problem, we study P-bearing species in diffuse/translucent clouds. In these objects phosphorus is mainly in…
We report here the first detection in the interstellar medium of the cyanomidyl radical (HNCN). Using the Yebes 40m and the IRAM 30m telescopes, we have targeted the doublets of the $N$=2$-$1, 4$-$3, 5$-$4, 6$-$5, and 7$-$6 transitions of HNCN toward the molecular cloud G+0.693-0.027. We have detected three unblended lines of HNCN, these are the $N$=6$-$5 doublet and one line of the $N$=4$-$3 transition. Additionally we present one line of the $N$=5$-$4 transition partially blended with emission from other species. The Local Thermodynamic Equilibrium best fit to the data gives a molecular abun…
To date, 204 individual molecular species, comprised of 16 different elements, have been detected in the interstellar and circumstellar medium by astronomical observations. These molecules range in size from two atoms to seventy, and have been detected across the electromagnetic spectrum from cm-wavelengths to the ultraviolet. This census presents a summary of the first detection of each molecular species, including the observational facility, wavelength range, transitions, and enabling laboratory spectroscopic work, as well as listing tentative and disputed detections. Tables of molecules det…
A quest for sulfur-bearing refractory species. Identification of CaS in the interstellar medium
Centro de Astrobiología (CAB), CSIC-INTA（天体生物学中心（CAB），西班牙国家研究委员会-国家航空航天技术研究所）；Institut de Ciències de l’Espai (ICE), CSIC（空间科学研究所（ICE），西班牙国家研究委员会）；Institut d’Estudis Espacials de Catalunya (IEEC)（加泰罗尼亚空间研究学院（IEEC））；Department of Astronomy, University of Florida（佛罗里达大学天文学系）；I. Physikalisches Institut, Universität zu Köln（科隆大学第一物理研究所）；Observatorio Astronómico Nacional (OAN)（国家天文台（OAN））
The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was thought before. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed "warm-up" scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures d…
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…
Cyanogen (NCCN) is the simplest member of the dicyanopolyynes group, and has been proposed as a major source of the CN radical observed in cometary atmospheres. Although not detected through its rotational spectrum in the cold interstellar medium, this very stable species is supposed to be very abundant. The chemistry of cyanogen in the cold interstellar medium can be investigated through its metastable isomer, CNCN (isocyanogen). Its formation may provide a clue on the widely abundant CN radical observed in cometary atmospheres. We performed an unbiased spectral survey of the L1544 proto-typi…
In order to understand grain-surface chemistry, one must have a good understanding of the reaction rate parameters. For diffusion-based reactions, these parameters are binding energies of the reacting species. However, attempts to estimate these values from grain-surface abundances using Bayesian inference are inhibited by a lack of enough sufficiently constraining data. In this work, we use the Massive Optimised Parameter Estimation and Data (MOPED) compression algorithm to determine which species should be prioritised for future ice observations to better constrain molecular binding energies…
There are different environments in the interstellar medium (ISM), depending on the density, temperature and chemical composition. Among them, molecular clouds, often referred to as the cradle of stars, are paradigmatic environments relative to the chemical diversity and complexity in space. Indeed, there, radio to far-infrared observations revealed the presence of several molecules in the gas phase, while near-infrared spectroscopy detected the existence of submicron sized dust grains covered by H2O -dominated ice mantles. The interaction between gas-phase species and the surfaces of water ic…
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)…
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…
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…
Context. Interstellar ice is the main form of metal species in dark molecular clouds. Experiments and observations have shown that the ice is significantly processed after the freeze-out of molecules onto grains. The processing is caused by cosmic-ray particles and cosmic-ray-induced UV photons. These transformations are included in current astrochemical models only to a very limited degree. Aims. We aim to establish a model of the "cold" chemistry in interstellar ices and to evaluate its general impact on the composition of interstellar ices. Methods. The ice was treated as consisting of two …
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 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. Cosmic ray particles that hit interstellar grains in dark molecular cores may induce whole-grain heating. The high temperature of a CR-heated grain allows energy barriers for bulk diffusion and reactions to be overcome. Additionally, ice molecules are destroyed by direct cosmic-ray induced dissociation. Aims. We provide a justified estimate of the significance of cosmic-ray induced surface-mantle diffusion, chemical reactions in ice, and dissociation of ice species in a star-forming interstellar cloud core. Methods. We considered a gas clump in a collapsing low-mass prestellar core an…
The evaporation of molecules from dust grains is crucial to understand some key aspects of the star- and the planet-formation processes. During the warm-up phase the presence of young protostellar objects induces molecules to evaporate from the dust surface into the gas phase, enhancing its chemical complexity. Similarly, in circumstellar disks, the position of the so-called snow-lines is determined by evaporation, with important consequences for the formation of planets. The amount of molecules that are desorbed depends on the interaction between the species and the grain surface, which is co…
Deuterium fractionation processes in the interstellar medium (ISM) have been shown to be highly efficient in the family of nitrogen hydrides. To date, observations were limited to ammonia (NH$_2$D, NHD$_2$, ND$_3$) and imidogen radical (ND) isotopologues. We want to explore the high frequency windows offered by the \emph{Herschel Space Observatory} to search for deuterated forms of amidogen radical NH$_2$ and to compare the observations against the predictions of our comprehensive gas-grain chemical model. Making use of the new molecular spectroscopy data recently obtained at high frequencies …
To date, 241 individual molecular species, comprised of 19 different elements, have been detected in the interstellar and circumstellar medium by astronomical observations. These molecules range in size from two atoms to seventy, and have been detected across the electromagnetic spectrum from cm-wavelengths to the ultraviolet. This census presents a summary of the first detection of each molecular species, including the observational facility, wavelength range, transitions, and enabling laboratory spectroscopic work, as well as listing tentative and disputed detections. Tables of molecules det…
Molecular nitrogen is one of the key species in the chemistry of interstellar clouds and protoplanetary disks and the partitioning of nitrogen between N and N2 controls the formation of more complex prebiotic nitrogen-containing species. The aim of this work is to gain a better understanding of the interstellar N2 photodissociation processes based on recent detailed theoretical and experimental work and to provide accurate rates for use in chemical models. We simulated the full high-resolution line-by-line absorption + dissociation spectrum of N2 over the relevant 912-1000 Å wavelength range, …
Polycyclic Aromatic Hydrocarbons (PAHs) are considered as a major constituent of interstellar dust. They have been proposed as the carriers of the Aromatic Infrared Bands (AIBs) observed in emission in the mid-IR. They likely have a significant contribution to various features of the extinction curve such as the 220 nm bump,the far-UV rise and the diffuse interstellar bands. Emission bands are also expected in the far-IR, which are better fingerprints of molecular identity than the AIBs. They will be searched for with the Herschel Space Observatory. Rotational emission is also expected in the …
Physical conditions in dense and cold regions of interstellar clouds favour the formation of ice mantles on the surfaces of interstellar grains. It is predicted that most of the gaseous species heavier than H2 or He will adsorb onto the grains and will disappear from the gas-phase, changing its chemistry, within 10^9/n_H years. Nonetheless, many molecules in molecular clouds are not completely depleted in timescales of 10^5 yr. Several speculative mechanisms have been proposed to explain why molecules stay in the gas phase, but up to now none are fully convincing. At the same time, these mecha…
