Context. Water together with O2 are important gas phase ingredients to cool dense gas in order to form stars. On dust grains, H2 O is an important constituent of the icy mantle in which a complex chemistry is taking place, as revealed by hot core observations. The formation of water can occur on dust grain surfaces, and can impact gas phase composition. Aims. The formation of molecules such as OH, H2 O, HO2, H2 O2, as well as their deuterated forms and O2 and O3 is studied in order to assess how the chemistry varies in different astrophysical environments, and how the gas phase is affected by grain surface chemistry. Methods. We use Monte Carlo simulations to follow the formation of molecules on bare grains as well as the fraction of molecules released into the gas phase. We consider a surface reaction network, based on gas phase reactions, as well as UV photo-dissociation of the chemical species. Results. We show that grain surface chemistry has a strong impact on gas phase chemistry, and that this chemistry is very different for different dust grain temperatures. Low temperatures favor hydrogenation, while higher temperatures favor oxygenation. Also, UV photons dissociate the molecules on the surface, that can reform subsequently. The formation-destruction cycle increases the amount of species released into the gas phase. We also determine the time scales to form ices in diffuse and dense clouds, and show that ices are formed only in shielded environments, as supported by observations.
Astrochemical modeling is needed for understanding the formation and evolution of interstellar molecules, and for extracting physical information from spectroscopic observations of interstellar clouds. The modeling usually involves handling of a chemical reaction network and solution of a set of coupled nonlinear ordinary differential equations, which is traditionally done using code written in compiled languages such as Fortran or C/C++. While being computationally efficient, there is room for improvement in the ease of use and interactivity for such an approach. In this work we present a new…
We present an observational and theoretical study of the primary ionizing agents (cosmic rays and X-rays) in the TW Hya protoplanetary disk. We use a set of resolved and unresolved observations of molecular ions and other molecular species, encompassing eleven lines total, in concert with a grid of disk chemistry models. The molecular ion constraints comprise new data from the Submillimeter Array on HCO$^+$, acquired at unprecedented spatial resolution, and data from the literature, including ALMA observations of N$_2$H$^+$. We vary the model incident CR flux and stellar X-ray spectra and find…
The deuterium fractionation of gas-phase molecules in hot cores is believed to reflect the composition of interstellar ices. The deuteration of methanol is a major puzzle, however, because the isotopologue ratio [CH2DOH]/[CH3OD], which is predicted to be equal to 3 by standard grain chemistry models, is much larger (~20) in low-mass hot corinos and significantly lower (~1) in high-mass hot cores. This dichotomy in methanol deuteration between low-mass and massive protostars is currently not understood. In this study, we report a simplified rate equation model of the deuterium chemistry occurri…
Dimethyl ether is one of the most abundant interstellar complex organic molecules. Yet its formation route remains elusive. In this work, we have performed electronic structure and kinetics calculations to derive the rate coefficients for two ion-molecule reactions recently proposed as a gas-phase formation route of dimethyl ether in interstellar objects, namely CH$_3$OH + CH$_3$OH$_2^+$ $\rightarrow$ (CH$_3$)$_2$OH$^+$ + H$_2$O followed by (CH$_3$)$_2$OH$^+$ + NH$_3$ $\rightarrow$ CH$_3$OCH$_3$ + NH$_4^+$. A comparison with previous experimental rate coefficients for the reaction CH$_3$OH + C…
An outstanding question of astrobiology is the link between the chemical composition of planets, comets, and other solar system bodies and the molecules formed in the interstellar medium. Understanding the chemical and physical evolution of the matter leading to the formation of protoplanetary disks is an important step for this. We provide some new clues to this long-standing problem using three-dimensional chemical simulations of the early phases of disk formation: we interfaced the full gas-grain chemical model Nautilus with the radiation-magnetohydrodynamic model RAMSES, for different conf…
Observations of diffuse clouds showed that they contain a number of simple hydrocarbons (e.g. CH, C$_2$H, (l- and c-)C$_3$H$_2$, and C$_4$H) in abundances that may be difficult to understand on the basis of conventional gas-phase chemical models. Recent experimental results revealed that the photo-decomposition mechanism of hydrogenated amorphous carbon (HAC) and of solid hexane releases a range of hydrocarbons into the gas, containing up to 6 C-atoms for the case of HAC decomposition. These findings motivated us to introduce a new potential input to interstellar chemistry; the "top-down" or d…
Recent years have witnessed the detection of an increasing number of complex organic molecules in interstellar space, some of them being of prebiotic interest. Disentangling the origin of interstellar prebiotic chemistry and its connection to biochemistry and ultimately to biology is an enormously challenging scientific goal where the application of complexity theory and network science has not been fully exploited. Encouraged by this idea, we present a theoretical and computational framework to model the evolution of simple networked structures toward complexity. In our environment, complex n…
The aim of the present work is to perform a comprehensive analysis of the interstellar chemistry of nitrogen, focussing on the gas-phase formation of the smallest polyatomic species and in particular nitrogen hydrides. We present a new chemical network in which the kinetic rates of critical reactions have been updated based on recent experimental and theoretical studies, including nuclear spin branching ratios. Our network thus treats the different spin symmetries of the nitrogen hydrides self-consistently together with the ortho and para forms of molecular hydrogen. This new network is used t…
Aims. Photodissociation by UV light is an important destruction mechanism for CO in many astrophysical environments, ranging from interstellar clouds to protoplanetary disks. The aim of this work is to gain a better understanding of the depth dependence and isotope-selective nature of this process. Methods. We present a photodissociation model based on recent spectroscopic data from the literature, which allows us to compute depth-dependent and isotope-selective photodissociation rates at higher accuracy than in previous work. The model includes self-shielding, mutual shielding and shielding b…
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…
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…
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…
University of Tokyo（东京大学）；Centro de Astrobiología (CAB), CSIC-INTA（天体生物学中心（CAB），西班牙国家航空航天技术研究所与西班牙国家科学研究委员会联合）；Max-Planck-Institut für extraterrestrische Physik（马克斯·普朗克地外物理研究所）
The presence of dust can strongly affect the chemical composition of the interstellar medium. We model the chemistry in photodissociation regions (PDRs) using both gas-phase and dust-phase chemical reactions. Our aim is to determine the chemical compositions of the interstellar medium (gas/dust/ice) in regions with distinct (molecular) gas densities that are exposed to radiation fields with different intensities. We have significantly improved the Meijerink PDR code by including 3050 new gas-phase chemical reactions and also by implementing surface chemistry. In particular, we have included 11…
Stars are bad neighbors: they often disturb their surroundings. They sometimes travel very fast through the interstellar medium (ISM). They frequently undergo violent ejection events which leave an imprint on their neighborhood (jets, winds, supernovae). These supersonic flows generate shocks both in the ejected material (bow shock) and in the stellar environment (termination shock). The global purpose of this thesis is to link the properties of stars and the ISM by studying these shocks. We model them with the Paris-Durham planar shock code, which incorporates a wealth of micro-physics and ch…
Benzonitrile (c-C6H5CN) has been recently detected in cold and dense regions of the interstellar medium (ISM), where it has been used as a signpost of a rich aromatic organic chemistry that might lead to the production of polycyclic aromatic hydrocarbons (PAHs). One possible origin of this benzonitrile is interstellar ice chemistry involving benzene (c-C6H6) and nitrile molecules (organic molecules containing the -CN group). We have addressed the plausibility of this c-C6H5CN formation pathway through laboratory experiments using our new setup SPACE TIGER. The SPACE TIGER experimental setup is…
Complex organic molecules, such as propylene (CH3CHCH2), are detected in molecular clouds (such as TMC1) with high fractional abundances (~2.10^{-9}, relative to hydrogen) that cannot be explained by gas-phase chemical reactions under normal dark cloud conditions. To obtain such high abundances requires an efficient grain-driven chemistry to be operating, coupled with effective desorption of the complex organics back into the gas-phase. We propose that the mechanism that we have previously described; rapid high density gas-phase chemistry in the gas released following sudden, total, ice mantle…
Interstellar ice mantles on the surfaces of dust grains are thought to have a bi-layered structure, with a H2O-rich polar layer, covered by a CO-rich apolar layer that probably harbors H2 and other volatiles such as N2. In this work, we explore the chemistry induced by 2 keV electrons and Ly-alpha photons in H2:CO:15N2 ice analogs of the CO-rich layer when exposed to similar fluences to those expected from the cosmic-ray-induced secondary electrons and UV photons during the typical lifetime of dense clouds. Six products were identified upon 2 keV electron irradiation: CO2, C2O (and other carbo…
In an effort to further our interest in understanding basic chemistry of interstellar molecules, we carry out here an extensive investigation of the stabilities of interstellar carbon chains; Cn, H2Cn, HCnN and CnX (X=N, O, Si, S, H, P, H-, N-). These sets of molecules accounts for about 20% of all the known interstellar and circumstellar molecules, their high abundances therefore demand a serious attention. High level ab initio quantum chemical calculations are employed to accurately estimate enthalpy of formation, chemical reactivity indices; global hardness and softness; and other chemical …
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 studi…
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…
AGB stars are, together with supernovae, the main contributors of stellar dust to the interstellar medium (ISM). Dust grains formed by AGB stars are thought to be large. However, as dust nucleation and growth within their outflows are still not understood, the dust-grain size distribution (GSD) is unknown. This is an important uncertainty regarding our knowledge of the chemical and physical history of interstellar dust, as AGB dust forms $\sim$ 70% of the starting point of its evolution. We expand on our chemical kinetics model, which uniquely includes a comprehensive dust-gas chemistry. The G…
Cis--Trans Rotational Isomerism of Seleno-, Thio-, and Formic Acids and Their Dimers: Chemical Kinetics under Interstellar Conditions
Department of Analytical, Biopharmaceutical and Medical Sciences, ATU, Galway, Ireland（爱尔兰高威应用科技大学分析、制药与医学科学系）；School of Biological & Chemical Sciences, University of Galway, Galway, Ireland（爱尔兰高威大学生物与化学科学学院）
Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. Especially, saturated, hydrogen-rich molecules are formed through surface chemistry. Astrochemical models have developed over the decades to understand the molecular processes in the interstellar medium, taking into account grain surface chemistry. 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…
Methane is one of the simplest stable molecules that is both abundant and widely distributed across space. It is thought to have partial origin from interstellar molecular clouds, which are near the beginning of the star formation cycle. Observational surveys of CH$_4$ ice towards low- and high-mass young stellar objects showed that much of the CH$_4$ is expected to be formed by the hydrogenation of C on dust grains, and that CH$_4$ ice is strongly correlated with solid H$_2$O. Yet, this has not been investigated under controlled laboratory conditions, as carbon-atom chemistry of interstellar …
