Context. The chemistry of the diffuse interstellar medium rests upon three pillars: exothermic ion-neutral reactions (" cold chemistry "), endothermic neutral-neutral reactions with significant activation barriers (" warm chemistry "), and reactions on the surfaces of dust grains. While warm chemistry becomes important in the shocks associated with turbulent dissipation regions, the main path for the formation of interstellar OH and H2O is that of cold chemistry. Aims. The aim of this study is to observationally confirm the association of atomic oxygen with both atomic and molecular gas phases, and to understand the measured abundances of OH and OH + as a function of the available reservoir of H2. Methods. We obtained absorption spectra of the ground states of OH, OH+ and OI with high-velocity resolution, with GREAT on-board SOFIA, and with the THz receiver at the APEX. We analyzed them along with ancillary spectra of HF and CH from HIFI. To deconvolve them from the hyperfine structure and to separate the blend that is due to various velocity components on the sightline, we fit model spectra consisting of an appropriate number of Gaussian profiles using a method combining simulated annealing with downhill simplex minimization. Together with HF and/or CH as a surrogate for H2, and HI $λ$21 cm data, the molecular hydrogen fraction f^N\_H2 = N(H 2)/(N(H) + 2N(H 2)) can be determined. We then investigated abundance ratios as a function of f^N\_H2. Results. The column density of OI is correlated at a high significance with the amount of available molecular and atomic hydrogen, with an atomic oxygen abundance of $3 \times 10 ^{-4}$ relative to H nuclei. While the velocities of the absorption features of OH and OH+ are loosely correlated and reflect the spiral arm crossings on the sightline, upon closer inspection they display an anticorrespondence. The arm-to-interarm density contrast is found to be higher in OH than in OH+. While both species can coexist, with a higher abundance in OH than in OH+, the latter is found less frequently in absence of OH than the other way around, which is a direct consequence of the rapid destruction of OH+ by dissociative recombination when not enough H2 is available. This conjecture has been substantiated by a comparison between the OH/OH+ ratio with f^N\_H2, showing a clear correlation. The hydrogen abstraction reaction chain OH+ (H2,H) H2O+ (H2,H)H3O+ is confirmed as the pathway for the production of OH and H 2 O. Our estimate of the branching ratio of the dissociative recombination of H3O+ to OH and H2O is confined within the interval of 84 to 91%, which matches laboratory measurements (74 to 83%). -- A correlation between the linewidths and column densities of OH+ features is found to be significant with a false-alarm probability below 5%. Such a correlation is predicted by models of interstellar MHD turbulence. For OH the same correlation is found to be insignificant because there are more narrow absorption features. Conclusions. While it is difficult to assess the contributions of warm neutral-neutral chemistry to the observed abundances, it seems fair to conclude that the predictions of cold ion-neutral chemistry match the abundance patterns we observed.
We propose a new simple computational model to estimate adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3P), nitrogen (4S), and oxygen (3P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14100 +- 420 K for carbon, 400 +- 30 K for nitrogen, and 1440 +-160 K for oxygen. The adsorption energy of oxygen is well consistent with experimentally reported value. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption…
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…
The primordial helium abundance $Y_P$ is calculated using sulphur as metallicity tracer in the classical methodology (with $Y_P$ as an extrapolation of $Y$ to zero metals). The calculated value, $Y_{P,\,S}=0.244\pm0.006$, is in good agreement with the estimate from the Planck experiment, as well as, determinations in the literature using oxygen as the metallicity tracer. The chemical analysis includes the sustraction of the nebular continuum and of the stellar continuum computed from simple stellar population synthesis grids. The $S^{+2}$ content is measured from the near infrared $\left[SIII\…
We present a summary of our previous investigations of the physical and chemical structure of the Horsehead nebula, and discuss how these studies led to advances on the understanding of the impact of FUV radiation on the structure of dense interstellar clouds. Specific molecular tracers can be used to isolate different environments, that are more sensitive to changes in the FUV radiation or density than the classical tracers of molecular gas : the CO isotopologues or the dust (sub)millimeter continuum emission. They include the HCO or CCH radicals for the FUV illuminated interfaces, or the mol…
We present spectroscopy of nine planetary nebulae (PNe) in the outskirts of M31, all but one obtained with the 10.4m GTC telescope. These sources extend our previous study of the oxygen abundance gradient of M31 to galactocentric radii as large as 100 kpc. None of the targets are bona fide members of a classical, metal-poor and ancient halo. Two of the outermost PNe have solar oxygen abundances, as well as radial velocities consistent with the kinematics of the extended disk of M31. The other PNe have a slightly lower oxygen content ([O/H] ~ -0.4) and in some cases large deviations from the di…
In this paper we use observations of molecular tracers in metal rich and alpha-enhanced galaxies to study the effect of abundance changes on molecular chemistry. We selected a sample of metal rich spiral and star bursting objects from the literature, and present here new data for a sample of early-type galaxies (ETGs). We conducted the first survey of CS and methanol emission in ETGs, detecting 7 objects in CS, and 5 in methanol emission. We find evidence to support the hypothesis that CS is a better tracer of dense star-forming gas than HCN. We suggest that the methanol emission in these sour…
We present experimental constraints on the insertion of oxygen atoms into methane to form methanol in astrophysical ice analogs. In gas-phase and theoretical studies this process has previously been demonstrated to have a very low or non-existent energy barrier, but the energetics and mechanisms have not yet been characterized in the solid state. We use a deuterium UV lamp filtered by a sapphire window to selectively dissociate O2 within a mixture of O2:CH4 and observe efficient production of CH3OH via O(1D) insertion. CH3OH growth curves are fit with a kinetic model, and we observe no tempera…
Turbulence is thought to be a key driver of the evolution of protoplanetary disks, regulating the mass accretion process, the transport of angular momentum, and the growth of dust particles. We intend to determine the magnitude of the turbulent motions in the outer parts (> 100 AU) of the disk surrounding DM Tau. Turbulent motions can be constrained by measuring the nonthermal broadening of line emission from heavy molecules. We used the IRAM Plateau de Bure interferometer to study emission from the CS molecule in the disk of DM Tau. High spatial (1.4 x 1 ") and spectral resolution (0.126 km/s…
To trace chemical evolution in a prototypical starburst environment, we spatially resolve the carbon and oxygen isotope ratios across the central molecular zone (full size ~$\sim 600$ pc) in the nearby starburst galaxy NGC 253. We imaged the emission of the optically thin isotopologues $^{13}$CO, C$^{18}$O, C$^{17}$O, $^{13}$C$^{18}$O at a spatial resolution $\sim50$ pc, comparable to the typical size of giant molecular associations. Optical depth effects and contamination of $^{13}$C$^{18}$O by C$_4$H is discussed and accounted for to derive column densities. This is the first extragalactic d…
We present the first identification in interstellar space of the thioformyl radical (HCS) and its metastable isomer HSC. These species were detected toward the molecular cloud L483 thanks to observations carried out with the IRAM 30m telescope in the 3 mm band. We derive beam-averaged column densities of 7e12 cm-2 for HCS and 1.8e11 cm-2 for HSC, which translate to fractional abundances relative to H2 of 2e-10 and 6e-12, respectively. Although the amount of sulfur locked by these radicals is low, their detection allows to put interesting constraints on the chemistry of sulfur in dark clouds. I…
Within the framework of The Heterogeneous dust Evolution Model at the IaS (THEMIS) this work investigates in detail the surface processes and chemistry relating to core/mantle interstellar and cometary grain structures and its influence on the nature of these fascinating particles. It appears that a realistic consideration of the nature and chemical reactivity of interstellar grain surfaces could self-consistently and within a coherent framework explain: the anomalous oxygen depletion, the nature of the CO dark gas, the formation of 'polar ice' mantles, the red wing on the 3 um water ice band,…
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 derive maps of the observed velocity of ionized gas, the oxygen abundance, and the extinction (Balmer decrement) across the area of the four spiral galaxies NGC36, NGC180, NGC6063, and NGC7653 from integral field spectroscopy obtained by the Calar Alto Legacy Integral Field Area (CALIFA) survey. We searched for spiral arms through Fourier analysis of the spatial distribution of three tracers (non-circular motion, enhancement of the oxygen abundance, and of the extinction) in the discs of our target galaxies. The spiral arms (two-armed logarithmic spirals in the deprojected map) are shown in…
Context. Several sulfur-bearing molecules are observed in the interstellar medium and in comets, in strong contrast to protoplanetary disks where only CS, H$_2$CS and SO have been detected so far. Aims. We combine observations and chemical models to constrain the sulfur abundances and their sensitivity to physical and chemical conditions in the DM Tau protoplanetary disk. Methods. We obtained $0.5^{"}$ ALMA observations of DM Tau in Bands 4 and 6 in lines of CS, SO, SO$_2$, OCS, CCS, H$_2$CS and H$_2$S, achieving a $\sim 5$ mJy sensitivity. Using the non-LTE radiative transfer code RADEX and t…
We combine Herschel observations of a total of 12 sources to construct the most uniform survey of HF and H2O in our Galactic disk. Both molecules are detected in absorption along all sight lines. The high spectral resolution of the Heterodyne Instrument for the Far-Infrared (HIFI) allows us to compare the HF and H2O distributions in 47 diffuse cloud components sampling the disk. We find that the HF and H2O velocity distributions follow each other almost perfectly and establish that HF and H2O probe the same gas-phase volume. Our observations corroborate theoretical predictions that HF is a sen…
We have observed 37 Infrared Dark Clouds (IRDCs), containing a total of 159 clumps, in high-density molecular tracers at 3 mm using the 22-meter ATNF Mopra Telescope located in Australia. After determining kinematic distances, we eliminated clumps that are not located in IRDCs and clumps with a separation between them of less than one Mopra beam. Our final sample consists of 92 IRDC clumps. The most commonly detected molecular lines are (detection rates higher than 8%): N2H+, HNC, HN13C, HCO+, H13CO+, HCN, C2H, HC3N, HNCO, and SiO. We investigate the behavior of the different molecular tracers…
The lines of HOC$^+$, HCO and CO$^+$ are considered good tracers of photon-dominated regions (PDRs) and X-ray dominated regions. We study these tracers towards regions of the Sgr B2 cloud selected to be affected by different heating mechanisms. We find the lowest values of the column density ratios of HCO$^+$ versus HOC$^+$, HCO and CO$^+$ in dense HII gas, where UV photons dominate the heating and chemistry of gas. HOC$^+$, HCO and CO$^+$ abundances and the above ratios are compared with those of chemical modeling, finding that high temperature chemistry, a cosmic-ray ionization rate of 10$^{…
For the first time, we establish a gas phase abundance pattern calibration for quiescent galaxies using optical emission lines. Quiescent galaxies have warm ionized gas showing line ratios similar to low-ionization nuclear emission line regions (LINER). The ionization mechanism for the gas is still an unsettled puzzle. Despite the uncertainty in the ionization mechanism, we argue that we can still infer certain gas phase abundance pattern from first principles. We show that the relative trend in N/O abundance can still be reliably measured based on [NII]6548,6583/[OII]3726,3729 and a direct me…
C+ is a key species in the interstellar medium but its 158 μm fine structure line cannot be observed from ground-based telescopes. Current models of fluorine chemistry predict that CF+ is the second most important fluorine reservoir, in regions where C+ is abundant. We detected the J = 1-0 and J = 2-1 rotational lines of CF+ with high signal-to-noise ratio towards the PDR and dense core positions in the Horsehead. Using a rotational diagram analysis, we derive a column density of N(CF+) = (1.5 - 2.0) \times 10^12 cm^-2. Because of the simple fluorine chemistry, the CF+ column density is propor…
We have investigated the role of molecular anion chemistry in pseudo-time dependent chemical models of dark clouds. With oxygen-rich elemental abundances, the addition of anions results in a slight improvement in the overall agreement between model results and observations of molecular abundances in TMC-1 (CP). More importantly, with the inclusion of anions, we see an enhanced production efficiency of unsaturated carbon-chain neutral molecules, especially in the longer members of the families CnH, CnH2, and HCnN. The use of carbon-rich elemental abundances in models of TMC-1 (CP) with anion ch…
Based on the occurrence rates implied by the discoveries of 1I/`Oumuamua and 2I/Borisov, the forthcoming Rubin Observatory Legacy Survey of Space and Time (LSST) should detect $\ge1$ interstellar objects every year (Hoover et al. 2021). We advocate for future measurements of the production rates of H$_2$O, CO$_2$ and CO in these objects to estimate their carbon to oxygen ratios, which traces formation locations within their original protoplanetary disks. We review similar measurements for Solar System comets, which indicate formation interior to the CO snowline. By quantifying the relative pro…
Prompted by the ongoing interest in Spitzer Infrared Spectrometer spectra of carbon stars in the Large Magellanic Cloud, we have investigated the circumstellar chemistry of carbon stars in low-metallicity environments. Consistent with observations, our models show that acetylene is particularly abundant in the inner regions of low metallicity carbon-rich AGB stars -- more abundant than carbon monoxide. As a consequence, larger hydrocarbons have higher abundances at the metallicities of the Magellanic Clouds than in stars with solar metallicity. We also find the oxygen and nitrogen chemistry is…
We have developed the first gas-grain chemical model for oxygen fractionation (also including sulphur fractionation) in dense molecular clouds, demonstrating that gas-phase chemistry generates variable oxygen fractionation levels, with a particularly strong effect for NO, SO, O2, and SO2. This large effect is due to the efficiency of the neutral 18O + NO, 18O + SO, and 18O + O2 exchange reactions. The modeling results were compared to new and existing observed isotopic ratios in a selection of cold cores. The good agreement between model and observations requires that the gas-phase abundance o…
Sub-arcsecond imaging of HCN and CN in the Orion Bar. UV-driven warm Nitrogen chemistry in dense environments
Instituto de Física Fundamental (CSIC)（基础物理研究所）；Institut de Radioastronomie Millimétrique（毫米波射电天文学研究所）；LUX, Observatoire de Paris, PSL Research University, CNRS, Sorbonne Universités（巴黎天文台）；Univ. Bordeaux, CNRS, Laboratoire d’Astrophysique de Bordeaux, UMR5804（波尔多大学）
Long-chain hydrocarbon anions CnH- (n=4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive ef…
We present a general parameter study, in which the abundance of interstellar argonium (ArH$^+$) is predicted using a model for the physics and chemistry of diffuse interstellar gas clouds. Results have been obtained as a function of UV radiation field, cosmic-ray ionization rate, and cloud extinction. No single set of cloud parameters provides an acceptable fit to the typical ArH$^+$, OH$^+$ and $\rm H_2O^+$ abundances observed in diffuse clouds within the Galactic disk. Instead, the observed abundances suggest that ArH$^+$ resides primarily in a separate population of small clouds of total vi…
The abundances of interstellar CH+ and SH+ are not well understood as their most likely formation channels are highly endothermic. Using data from Herschel, we study the formation of CH+ and SH+ in a typical high UV-illumination photon-dominated region (PDR), the Orion Bar. Herschel/HIFI provides velocity-resolved data of CH+ 1-0 and 2-1 and three hyperfine transitions of SH+. Herschel/PACS provides information on the excitation and spatial distribution of CH+ (up to J=6-5). The widths of the CH+ 2-1 and 1-0 transitions are of ~5 km/s, significantly broader than the typical width of dense gas …
We study ten molecular transitions obtained from an unbiased 3 mm molecular line survey using the IRAM 30 m telescope toward 409 compact dust clumps identified by the APEX Telescope Large Area Survey of the Galaxy (ATLASGAL) to understand photodissociation regions (PDRs) associated with the clumps. The main goal of this study is to investigate whether the abundances of the selected molecules show any variations resulting from the PDR chemistry in different clump environments. We selected HCO, HOC$^+$, C$_{2}$H, c-C$_{3}$H$_{2}$, CN, H$^{13}$CN, HC$^{15}$N, and HN$^{13}$C as PDR tracers, and H$…
As material from an infalling protostellar envelope hits the forming disk, an accretion shock may develop which could (partially) alter the envelope material entering the disk. Observations with the Atacama Large Millimeter/submillimeter Array (ALMA) indicate that emission originating from warm SO and SO$_2$ might be good tracers of such accretion shocks. The goal of this work is to test under what shock conditions the abundances of gas-phase SO and SO$_2$ increase in an accretion shock at the disk-envelope interface. Detailed shock models including gas dynamics are computed using the Paris-Du…
Recent water line observations toward several low-mass protostars suggest low water gas fractional abundances in the inner warm envelopes. Water destruction by X-rays has been proposed to influence the water abundances in these regions, but the detailed chemistry, including the nature of alternative oxygen carriers, is not yet understood. In this study, we aim to understand the impact of X-rays on the composition of low-mass protostellar envelopes, focusing specifically on water and related oxygen bearing species. We compute the chemical composition of two low-mass protostellar envelopes using…
We present for the first time a detailed study of the properties of molecular gas in metal-rich environments such as early-type galaxies (ETGs). We have explored Photon-Dominated Region (PDR) chemistry for a wide range of physical conditions likely to be appropriate for these sources. We derive fractional abundances of the 20 most chemically reactive species as a function of the metallicity, as a function of the optical depth and for various volume number gas densities, Far-Ultra Violet (FUV) radiation fields and cosmic ray ionisation rates. We also investigate the response of the chemistry to…
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…
The energy to desorb atomic oxygen from an interstellar dust grain surface, $E_{\rm des}$, is an important controlling parameter in gas-grain models; its value impacts the temperature range over which oxygen resides on a dust grain. However, no prior measurement has been done of the desorption energy. We report the first direct measurement of $E_{\rm des}$ for atomic oxygen from dust grain analogs. The values of $E_{\rm des}$ are $1660\pm 60$~K and $1850\pm 90$~K for porous amorphous water ice and for a bare amorphous silicate film, respectively, or about twice the value previously adopted in …
Understanding the chemistry of the interstellar medium (ISM) is fundamental for the comprehension of the Galactic and stellar evolution. X-rays provide an excellent way to study the dust chemical composition and crystallinity along different sight-lines in the Galaxy. In this work we study the dust grain chemistry in the diffuse regions of the interstellar medium in the soft X-ray band (<1 keV). We use newly calculated X-ray dust extinction cross sections, obtained from laboratory data, in order to investigate the oxygen K and iron L shell absorption. We explore the XMM-Newton and Chandra spec…
Observations of high-redshift quasars provide information on the massive black holes (MBHs) powering them and the galaxies hosting them. Current observations of $z \gtrsim 6$ hosts, at sub-mm wavelengths, trace the properties of cold gas, and these are used to compare with the correlations between MBHs and galaxies characterising the $z=0$ population. The relations at $z=0$, however, rely on stellar-based tracers of the galaxy properties. We perform a very-high resolution cosmological zoom-in simulation of a $z=7$ quasar including state-of-the-art non-equilibrium chemistry, MBH formation, grow…
Advances in infrared and submillimeter technology have allowed for detailed observations of the molecular content of the planet-forming regions of protoplanetary disks. In particular, disks around solar-type stars now have growing molecular inventories that can be directly compared with both prestellar chemistry and that inferred for the early solar nebula. The data directly address the old question whether the chemistry of planet-forming matter is similar or different and unique relative to the chemistry of dense clouds and protostellar envelopes. The answer to this question may have profound…
