We present astrochemical photo-dissociation region models in which cosmic ray attenuation has been fully coupled to the chemical evolution of the gas. We model the astrochemical impact of cosmic rays, including those accelerated by protostellar accretion shocks, on molecular clouds hosting protoclusters. Our models with embedded protostars reproduce observed ionization rates. We study the imprint of cosmic ray attenuation on ions for models with different surface cosmic ray spectra and different star formation efficiencies. We find that abundances, particularly ions, are sensitive to the treatment of cosmic rays. We show the column densities of ions are under predicted by the `classic' treatment of cosmic rays by an order of magnitude. We also test two common chemistry approximations used to infer ionization rates. We conclude that the approximation based on the H$_3^+$ abundance under predicts the ionization rate except in regions where the cosmic rays dominate the chemistry. Our models suggest the chemistry in dense gas will be significantly impacted by the increased ionization rates, leading to a reduction in molecules such as NH$_3$ and causing H$_2$-rich gas to become [C II] bright.
We utilize a modified astrochemistry code which includes cosmic ray attenuation in-situ to quantify the impact of different cosmic-ray models on the CO-to-H$_2$ and CI-to-H$_2$ conversion factors, $X_{\rm CO}$ and $X_{\rm CI}$, respectively. We consider the impact of cosmic rays accelerated by accretion shocks, and show that clouds with star formation efficiencies greater than 2\% have $X_{\rm CO} = (2.5 \pm 1)\times10^{20}$ cm$^{-2}$(K km s$^{-1}$)$^{-1}$, consistent with Milky Way observations. We find that changing the cosmic ray ionization rate from external sources from the canonical $ζ\a…
The origin of bistable solutions in the kinetic equations describing the chemistry of dense interstellar clouds is explained as being due to the autocatalysis and feedback of oxygen nuclei from the oxygen dimer (O2). We identify four autocatalytic processes that can operate in dense molecular clouds, driven respectively by reactions of H+, He+, C+, and S+ with O2. We show that these processes can produce the bistable solutions found in previous studies, as well as the dependence on various model parameters such as the helium ionization rate, the sulfur depletion and the {H}3+ electron recombin…
Many astrochemical models today explicitly consider the species that comprise the bulk of interstellar dust grain ice-mantles separately from those in the top few monolayers. Bombardment of these ices by ionizing radiation - whether in the form of cosmic rays, stellar winds, or radionuclide emission - represents an astrochemically viable means of driving a rich chemistry even in the bulk of the ice-mantle, now supported by a large body of work in laboratory astrophysics. In this study, using an existing rate equation-based astrochemical code modified to include a method of considering radiatio…
We have revisited the chemistry of chlorine-bearing species in the diffuse interstellar medium with new observations of the HCl$^+$ 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 …
Positive ions play a fundamental role in the interstellar chemistry, especially in cold environments where chemistry is believed to be mainly ion-driven. However, in contrast with neutral species, most of the cations present in the astrochemical reaction networks are not fully characterized in the astrochemical literature. To fill up this gap, we have carried out new accurate quantum chemical calculations to identify the structures and energies of 262 cations with up to 14 atoms that are postulated to have a role in the interstellar chemistry. Optimised structures and rotational constants were…
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））
The initial stage of star formation is a complex area study because of its high density and low temperature. Under such conditions, many molecules become depleted from the gas phase by freezing out onto dust grains. However, the deuterated species could remain gaseous and are thus ideal tracers. We investigate the gas dynamics and NH$_2$D chemistry in eight massive pre/protocluster clumps. We present NH$_2$D 1$_{11}$-1$_{01}$ (at 85.926 GHz), NH$_3$ (1, 1) and (2, 2) observations in the eight clumps using the PdBI and the VLA, respectively. We find that the distribution between deuterium fract…
In external galaxies, molecular composition may be influenced by extreme environments such as starbursts and galaxy mergers. To study such molecular chemistry, we observed the luminous-infrared galaxy and merger NGC 3256 using the Atacama Large Millimeter/sub-millimeter Array. We covered most of the 3-mm and 1.3-mm bands for a multi-species, multi-transition analysis. We first analyzed intensity ratio maps of selected lines such as HCN/HCO$^+$, which shows no enhancement at an AGN. We then compared the chemical compositions within NGC 3256 at the two nuclei, tidal arms, and positions with infl…
Quantum mechanical tunneling of atoms is increasingly found to play an important role in many chemical transformations. Experimentally, atom-tunneling can be indirectly detected by temperature-independent rate constants at low temperature or by enhanced kinetic isotope effects. On the contrary, using computational investigations the influence of tunneling on the reaction rates can directly be monitored. The tunnel effect, for example, changes reaction paths and branching ratios, enables chemical reactions in an astrochemical environment that would be impossible by thermal transition, and influ…
Predictions of astrochemical models depend strongly on the reaction rate coefficients used in the simulations. We reviewed a number of key reactions for the chemistry of nitrogen-bearing species in the dense interstellar medium and proposed new reaction rate coefficients for those reactions. The details of the reviews are given in the form of a datasheet associated with each reaction. The new recommended rate coefficients are given with an uncertainty and a temperature range of validity and will be included in KIDA (http://kida.obs.u-bordeaux1.fr).
L1157-B1 is the brightest shocked region of the large-scale molecular outflow, considered the prototype of chemically rich outflows, being the ideal laboratory to study how shocks affect the molecular gas. Several deuterated molecules have been previously detected with the IRAM 30m, most of them formed on grain mantles and then released into the gas phase due to the shock. We aim to observationally investigate the role of the different chemical processes at work that lead to formation the of DCN and test the predictions of the chemical models for its formation. We performed high-angular resolu…
Testing various assumptions for radiolysis, non-diffusive chemistry, and chemical desorption in cold cores
Laboratoire d’astrophysique de Bordeaux, Univ. Bordeaux, CNRS（波尔多天体物理学实验室，波尔多大学，法国国家科学研究中心）；School of Astronomy & Space Science, Nanjing University（南京大学天文与空间科学学院）
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…
The ionization fraction plays a key role in the physics and chemistry of the neutral interstellar medium, from controlling the coupling of the gas to the magnetic field to allowing fast ion-neutral reactions that drive interstellar chemistry. Most estimations of the ionization fraction have relied on deuterated species such as DCO+, whose detection is limited to dense cores representing an extremely small fraction of the volume of the giant molecular clouds they are part of. As large field-of-view hyperspectral maps become available, new tracers may be found. We search for the best observable …
We present a new high-resolution study of pre-protocluster regions in tracers exclusively probing the coldest and dense gas (NH_2D). The data are used to constrain the chemical, thermal, kinematic, and physical conditions (i.e., densities) in G29.96e and G35.20w. NH_3, NH_2D, and continuum emission were mapped using the VLA, and PdBI. In particular, NH_2D is a unique tracer of cold, precluster gas at high densities, while NH_3 traces both the cold and warm gas of modest-to-high densities. In G29.96e, Spitzer images reveal two massive filaments, one of them in extinction (infrared dark cloud). …
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…
In this paper, we present preliminary results illustrating the effect of cosmic rays on solid-phase chemistry in models of both TMC-1 and several sources with physical conditions identical to TMC-1 except for hypothetically enhanced ionization rates. Using a recent theory for the addition of cosmic ray-induced reactions to astrochemical models, we calculated the radiochemical yields, called $G$ values, for the primary dust grain ice-mantle constituents. We show that the inclusion of this non-thermal chemistry can lead to the formation of complex organic molecules from simpler ice-mantle consti…
A continuous supersonic flow reactor has been used to measure rate constants for the C + NH3 reaction over the temperature range 50 to 296 K. C atoms were created by the pulsed laser photolysis of CBr4. The kinetics of the title reaction were followed directly by vacuum ultra-violet laser induced fluorescence (VUV LIF) of C loss and through H formation. The experiments show unambiguously that the reaction is rapid at 296 K, becoming faster at lower temperatures, reaching a value of 1.8 10-10 cm3 molecule-1 s-1 at 50 K. As this reaction is not currently included in astrochemical networks, its i…
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…
Our current understanding of interstellar carbon fractionation hinges on the interpretation of astrochemical kinetic models. Yet, the various reactions included carry large uncertainties in their (estimated) rate coefficients, notably those involving C with C$_{2}$. In this work, we provide theoretical thermal rate coefficients as a function of the temperature for all possible gas-phase isotope-exchange reactions of C+C$_{2}(X^{1}Σ_{g}^{+},a^{3}Π_{u})$. For this, we employ the quasi-classical trajectory method, with the previously obtained potential energy surfaces of C$_{3}$ dictating the for…
[Context] Two competing models describe the formation of massive stars in objects like the Orion Trapezium. In the turbulent core accretion model, the resulting stellar masses are directly related to the mass distribution of the cloud condensations. In the competitive accretion model, the gravitational potential of the protocluster captures gas from the surrounding cloud for which the individual cluster members compete. [Aims] With high resolution submillimeter observations of the structure, kinematics, and chemistry of the proto-Trapezium cluster W3 IRS5, we aim to determine which mode of sta…
Context: It has been proposed that H$_2$ near-infrared lines may be excited by cosmic rays and allow for a determination of the cosmic-ray ionization rate in dense gas. One-dimensional models show that measuring both the H$_2$ gas column density and H$_2$ line intensity enables a constraint on the cosmic-ray ionization rate as well as the spectral slope of low-energy cosmic-ray protons in the interstellar medium (ISM). Aims: We aim to investigate the impact of certain assumptions regarding the H$_2$ chemical models and ISM density distributions on the emission of cosmic-ray induced H$_2$ emiss…
A wide variety of molecules have recently been detected in the Horsehead nebula photodissociation region (PDR) suggesting that: (i) gas-phase and grain chemistries should both contribute to the formation of organic molecules, and (ii) far-ultraviolet (FUV) photodesorption may explain the release into the gas phase of grain surface species. In order to tackle these specific problems and more generally in order to better constrain the chemical structure of these types of environments we present a study of the Horsehead nebula gas-grain chemistry. To do so we used the 1D astrochemical gas-grain c…
The chemistry of dense interstellar regions was analyzed using a time-dependent gas-grain astrochemical simulation and a new chemical network that incorporates deuterated chemistry taking into account nuclear spin-states for the hydrogen chemistry and its deuterated isotopologues. With this new network, the utility of the [HCO$^+$]/[DCO$^+$] abundance ratio as a probe of the cosmic ray ionization rate has been reexamined, with special attention paid to the effect of the initial value of the molecular hydrogen ortho-to-para ratio (OPR). After discussing the use of the probe for cold cores, we t…
Grain surface chemistry and its treatment in gas-grain chemical models is an area of large uncertainty. Whilst laboratory experiments are making progress, there is still much that is unknown about grain surface chemistry. Further, the results and parameters produced by experiment are often not easily translated to the rate equation approach most commonly used in astrochemical modelling. It is possible that statistical methods can reduce the uncertainty in grain surface chemical networks. In this work, a simple model of grain surface chemistry in a molecular cloud is developed and a Bayesian in…
The impact of attenuation on cosmic-ray chemistry: I. Abundances and chemical calibrators in molecular clouds
Chalmers University of Technology（查尔姆斯理工大学）；Indian Institute of Science Education and Research Kolkata（印度科学教育研究所加尔各答分校）；University of Duisburg-Essen（杜伊斯堡-埃森大学）；University of Virginia（弗吉尼亚大学）
In this work, we reexamine sulfur chemistry occurring on and in the ice mantles of interstellar dust grains, and report the effects of two new modifications to standard astrochemical models; namely, (a) the incorporation of cosmic ray-driven radiation chemistry and (b) the assumption of fast, non-diffusive reactions for key radicals in the bulk. Results from our models of dense molecular clouds show that these changes can have a profound influence on the abundances of sulfur-bearing species in ice mantles, including a reduction in the abundance of solid-phase H$_2$S and HS, and a significant i…
NeuralPDR: Neural Differential Equations as surrogate models for Photodissociation Regions
Leiden Observatory, Leiden University（莱顿天文台，莱顿大学）；SURF；Research Center for Astronomical Computing, Zhejiang Lab（天文计算研究中心，浙江实验室）；Transdisciplinary Research Area (TRA) ‘Matter’/Argelander-Institut für Astronomie, University of Bonn（跨学科研究领域（TRA）‘物质’/阿格拉德勒天文台研究所，波恩大学）；Department of Physics and Astronomy, University College London（物理与天文学系，伦敦大学学院）
The Galactic centre G+0.633-0.0604 molecular cloud: A new astrochemical gold mine: II. Chemical richness
Centro de Astrobiología (CAB), CSIC-INTA（天体生物学中心）；Universidad Complutense de Madrid（马德里康普顿斯大学）；Max-Planck-Institut für extraterrestrische Physik（马克斯·普朗克地外物理研究所）；European Southern Observatory（欧洲南方天文台）；Joint ALMA Observatory（ALMA联合天文台）；RIKEN（理化学研究所）
Heating of whole interstellar dust grains by cosmic-ray (CR) particles affects the gas-grain chemistry in molecular clouds by promoting molecule desorption, diffusion, and chemical reactions on grain surfaces. The frequency of such heating $f_T$, s$^{-1}$, determines how often a certain temperature $T_{\rm CR}$, K, is reached for grains hit by CR particles. This study aims to provide astrochemists with comprehensive and updated dataset on the CR-induced whole-grain heating. We present calculations of $f_T$ and $T_{\rm CR}$ spectra for bare olivine grains with radius $a$ of 0.05; 0.1; 0.2 $μ$m,…
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 …
Among all the interstellar complex organic molecules (iCOMs), acetaldehyde is one of the most widely detected species. The question of its formation route(s) is, therefore, of a major interest regarding astrochemical models. In this paper, we provide an extensive review of the gas-phase formation paths that were, or are, reported in the literature and the major astrochemical databases. Four different gas-phase formation routes stand out : (1) CH$_3$OCH$_3$ + H$^+$ / CH$_3$CHOH$^+$ + e$^-$, (2) C$_2$H$_5$ + O($^3$P), (3) CH$_3$OH + CH and (4) CH$_3$CH$_2$OH + OH / CH$_3$CHOH + O($^3$P). Paths (…
We study the gravitational collapse of prestellar sources and the associated evolution of their chemical composition. We use the University of Grenoble Alpes Astrochemical Network (UGAN), which includes reactions involving the different nuclear--spin states of H2, H3+, and of the hydrides of carbon, nitrogen, oxygen, and sulfur, for reactions involving up to seven protons. In addition, species-to-species rate coefficients are provided for the ortho/para interconversion of the H3+ + H2 system and isotopic variants. The composition of the medium is followed from an initial steady state through t…
The Galactic Centre G+0.633-0.0604 Molecular Cloud: A New Gold Mine for Astrochemistry
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/西班牙国家科学研究委员会）；Center for Astrochemical Studies, Max-Planck-Institut für extraterrestrische Physik（系外行星物理研究所天体化学研究）
The chemistry in the diffuse interstellar medium initiates the gradual increase of molecular complexity during the life cycle of matter. A key molecule that enables build-up of new molecular bonds and new molecules via proton-donation is H3+. Its evolution is tightly related to molecular hydrogen and thought to be well understood. However, recent observations of ortho and para lines of H2 and H3+ in the diffuse ISM showed a puzzling discrepancy in nuclear spin excitation temperatures and populations between these two key species. H3+, unlike H2, seems to be out of thermal equilibrium, contrary…
Massive star-forming regions exhibit an extremely rich and diverse chemistry, which in principle provides a wealth of molecular probes, as well as laboratories for interstellar prebiotic chemistry. Since the chemical structure of these sources displays substantial spatial variation among species on small scales (${\lesssim}10^4$ au), high angular resolution observations are needed to connect chemical structures to local environments and inform astrochemical models of massive star formation. To address this, we present ALMA 1.3 mm observations toward OB cluster-forming region G10.6-0.4 (hereaft…
We present the results of chemical modeling of complex organic molecules (COMs) under conditions typical for prestellar cores. We utilize an advanced gas-grain astrochemical model with updated gas-phase chemistry, with a multilayer approach to ice-surface chemistry and an up-to-date treatment of reactive desorption based on recent experiments of Minissale et al. (2016). With the chemical model, radial profiles of molecules including COMs are calculated for the case of the prototypical prestellar core L1544 at the timescales when the modeled depletion factor of CO becomes equal to that observed…
We present the first gas-grain astrochemical model of the NGC 2264 CMM3 protostellar core. The chemical evolution of the core is affected by changing its physical parameters such as the total density and the amount of gas-depletion onto grain surfaces as well as the cosmic ray ionisation rate, $ζ$. We estimated $ζ_{\text {CMM3}}$ = 1.6 $\times$ 10$^{-17}$ s$^{-1}$. This value is 1.3 times higher than the standard CR ionisation rate, $ζ_{\text {ISM}}$ = 1.3 $\times$ 10$^{-17}$ s$^{-1}$. Species response differently to changes into the core physical conditions, but they are more sensitive to cha…
