The nuclear-spin chemistry of interstellar water is investigated using the University of Grenoble Alpes Astrochemical Network (UGAN). This network includes reactions involving the different nuclear-spin states of the hydrides of carbon, nitrogen, oxygen and sulphur, as well as their deuterated forms. Nuclear-spin selection rules are implemented within the scrambling hypothesis for reactions involving up to seven protons. The abundances and ortho-to-para ratios (OPRs) of gas-phase water and water ions (H$_2$O$^+$ and H$_3$O$^+$) are computed under the steady-state conditions representative of a dark molecular cloud and during the early phase of gravitational collapse of a prestellar core. The model incorporates the freezing of the molecules on to grains, simple grain surface chemistry and cosmic-ray induced and direct desorption of ices. The predicted OPRs are found to deviate significantly from both thermal and statistical values and to be independent of temperature below $\sim $30~K. The OPR of H$_2$O is shown to lie between 1.5 and 2.6, depending on the spin-state of H$_2$, in good agreement with values derived in translucent clouds with relatively high extinction. In the prestellar core collapse calculations, the OPR of H$_2$O is shown to reach the statistical value of 3 in regions with severe depletion ($n_{\rm H}> 10^7$~cm$^{-3}$). We conclude that a low water OPR ($\lesssim 2.5$) is consistent with gas-phase ion-neutral chemistry and reflects a gas with OPR(H$_2)\lesssim 1$. Available OPR measurements in protoplanetary disks and comets are finally discussed.
Interstellar dark clouds are the sites of star formation. Their main component, dihydrogen, exists under two states, ortho and para. H2 is supposed to form in the ortho:para ratio (OPR) of 3:1 and to subsequently decay to almost pure para-H2 (OPR <= 0.001). Only if the H2 OPR is low enough, will deuteration enrichment, as observed in the cores of these clouds, be efficient. The second condition for strong deuteration enrichment is the local disappearance of CO, which freezes out onto grains in the core formation process. We show that this latter condition does not apply to DCO+, which, therefo…
Context: Fast surface conversion between ortho- and para-H2 has been observed in laboratory studies, and this mechanism has been proposed to play a role in the control of the ortho-para ratio in the interstellar medium. Observations of rotational lines of H2 in Photo-Dissociation Regions (PDRs) have indeed found significantly lower ortho-para ratios than expected at equilibrium. The mechanisms controlling the balance of the ortho-para ratio in the interstellar medium thus remain incompletely understood, while this ratio can affect the thermodynamical properties of the gas (equation of state, c…
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…
The ultraviolet and far--ultraviolet spectra of HD 147888 allows to access the v=0 as well as higher vibrational levels of the ground H2 electronic level. We have determined column densities of the H2 molecule on vibrational levels v=0-5 and rotational levels J=0-6. The ortho to para H2 ratio for the excited vibrational states equals to 1.2. For the lowest vibrational state v=0 and rotational level J=1 the ortho to para H2 ratio is only 0.16. The temperature of ortho-para thermodynamical equilibrium is T_OP=43+-3 K. The large number of H2 absorption lines in the HST spectra allows to determine…
We present an analysis of interstellar H2 toward HD 37903, which is a hot, B 1.5 V star located in the NGC 2023 reflection nebula. Meyer et al. (2001) have used a rich spectrum of vibrationally excited H2 observed by the HST to calculate a model of the interstellar cloud toward HD 37903. We extend Mayer's analysis by including the v"=0 vibrational level observed by the FUSE satellite. The T01 temperature should not be interpreted as a rotational temperature, but rather as a temperature of thermal equilibrium between the ortho and para H2. The ortho to para H2 ratio is lower for collisionally p…
We report on the detection of the ground-state rotational line of ortho-D2H+ at 1.477 THz (203 micron) using the German REceiver for Astronomy at Terahertz frequencies (GREAT) onboard the Stratospheric Observatory For Infrared Astronomy (SOFIA). The line is seen in absorption against far-infrared continuum from the protostellar binary IRAS 16293-2422 in Ophiuchus. The para-D2H+ line at 691.7 GHz was not detected with the APEX telescope toward this position. These D2H+ observations complement our previous detections of para-H2D+ and ortho-H2D+ using SOFIA and APEX. By modeling chemistry and rad…
We report additional detections of the chloronium molecular ion, H$_2$Cl$^+$, toward four bright submillimeter continuum sources: G29.96, W49N, W51, and W3(OH). With the use of the HIFI instrument on the Herschel Space Observatory, we observed the $2_{12}-1_{01}$ transition of ortho-H$_2^{35}$Cl$^+$ at 781.627 GHz in absorption toward all four sources. Much of the detected absorption arises in diffuse foreground clouds that are unassociated with the background continuum sources and in which our best estimates of the $N({\rm H_2Cl^+})/N({\rm H})$ ratio lie in the range $(0.9 - 4.8) \times 10^{-…
Based on recent $Herschel$ results, the ortho-to-para ratio (OPR) of NH$_2$ has been measured towards the following high-mass star-forming regions: W31C (G10.6-0.4), W49N (G43.2-0.1), W51 (G49.5-0.4), and G34.3+0.1. The OPR at thermal equilibrium ranges from the statistical limit of three at high temperatures to infinity as the temperature tends toward zero, unlike the case of H$_{2}$. Depending on the position observed along the lines-of-sight, the OPR was found to lie either slightly below the high temperature limit of three (in the range $2.2-2.9$) or above this limit ($\sim3.5$, $\gtrsim 4…
A continuous supersonic flow reactor has been used to measure rate constants for the C + NH3 reaction over the temperature range 50 to 296 K. C atoms were created by the pulsed laser photolysis of CBr4. The kinetics of the title reaction were followed directly by vacuum ultra-violet laser induced fluorescence (VUV LIF) of C loss and through H formation. The experiments show unambiguously that the reaction is rapid at 296 K, becoming faster at lower temperatures, reaching a value of 1.8 10-10 cm3 molecule-1 s-1 at 50 K. As this reaction is not currently included in astrochemical networks, its i…
We report the first detection in interstellar space of the 3-cyano propargyl radical (CH2C3N). This species was observed in the cold dark cloud TMC-1 using the Yebes 40m telescope. A total of seven rotational transitions for both ortho- and para-CH2C3N species were observed in the 31.0-50.4 GHz range. We derive a total column density of (1.6 +/- 0.4)e11 cm-2 and an ortho/para ratio of 2.4 +/- 1.2, which implies an abundance ratio CH2C3N/CH3C3N around 0.1, in sharp contrast with the smaller analogues, in which case CH2CN/CH3CN = 3. This indicates that the chemistry of the cyanides CH2C3N and CH…
Spectral line surveys reveal rich molecular reservoirs in G331.512-0.103, a compact radio source in the center of an energetic molecular outflow. In this first work, we analyse the physical conditions of the source by means of CH$_3$OH and CH$_3$CN. The observations were performed with the APEX telescope. Six different system configurations were defined to cover most of the band within (292-356) GHz; as a consequence we detected a forest of lines towards the central core. A total of 70 lines of $A/E$-CH$_3$OH and $A/E$-CH$_3$CN were analysed, including torsionally excited transitions of CH$_3$…
The detection of CF$^+$ in interstellar clouds potentially allows astronomers to infer the elemental fluorine abundance and the ionization fraction in ultraviolet-illuminated molecular gas. Because local thermodynamic equilibrium (LTE) conditions are hardly fulfilled in the interstellar medium (ISM), the accurate determination of the CF$^+$ abundance requires one to model its non-LTE excitation via both radiative and collisional processes. Here, we report quantum calculations of rate coefficients for the rotational excitation of CF$^+$ in collisions with para- and ortho-H2 (for temperatures up…
Using the Herschel Space Observatory's Heterodyne Instrument for the Far-Infrared (HIFI), we have observed para-chloronium (H2Cl+) toward six sources in the Galaxy. We detected interstellar chloronium absorption in foreground molecular clouds along the sight-lines to the bright submillimeter continuum sources Sgr A (+50 km/s cloud) and W31C. Both the para-H2-35Cl+ and para-H2-37Cl+ isotopologues were detected, through observations of their 1(11)-0(00) transitions at rest frequencies of 485.42 and 484.23 GHz, respectively. For an assumed ortho-to-para ratio of 3, the observed optical depths imp…
The HIFI instrument on board the Herschel Space Observatory has been used to observe interstellar nitrogen hydrides along the sight-line towards G10.6-0.4 in order to improve our understanding of the interstellar chemistry of nitrogen. We report observations of absorption in NH N=1-0, J=2-1 and ortho-NH2 1_1,1-0_0,0. We also observed ortho-NH3 1_0-0_0, and 2_0-1_0, para-NH3 2_1-1_1, and searched unsuccessfully for NH+. All detections show emission and absorption associated directly with the hot-core source itself as well as absorption by foreground material over a wide range of velocities. All…
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…
We report the detection of absorption by interstellar hydroxyl cations and water cations, along the sight-line to the bright continuum source W49N. We have used Herschel's HIFI instrument, in dual beam switch mode, to observe the 972 GHz N = 1 - 0 transition of OH+ and the 1115 GHz 1(11) - 0(00) transition of ortho-H2O+. The resultant spectra show absorption by ortho-H2O+, and strong absorption by OH+, in foreground material at velocities in the range 0 to 70 km/s with respect to the local standard of rest. The inferred OH+/H2O+ abundance ratio ranges from ~ 3 to ~ 15, implying that the observ…
Hydronium (H$_3$O$^+$) was first detected in 1986 in interstellar molecular clouds. It was reported in many galactic diffuse and dense regions, as well as in extragalactic sources. H$_3$O$^+$ plays a major role both in interstellar oxygen and water chemistry. However, despite the large number of H$_3$O$^+$ observations, its collisional excitation was investigated only partially. In the present work we study the state-to-state rotational de-excitation of $ortho$- and $para$-H$_3$O$^+$ in collisions both with $ortho$- and $para$-H$_2$. The cross sections are calculated within the close-coupling …
The ortho-to-para ratio (OPR) of H$_2$O is thought to be sensitive to the temperature of water formation. The OPR of H$_2$O is thus useful to study the formation mechanism of water. We investigate the OPR of water in the Orion PDR (Photon-dominated region), at the Orion Bar and Orion S positions, using data from {\it Herschel}/HIFI. We detect the ground-state lines of ortho- and para-H$_2$$^{18}$O in the Orion Bar and Orion S and we estimate the column densities using LTE and non-LTE methods. Based on our calculations, the ortho-to-para ratio (OPR) in the Orion Bar is 0.1 $-$ 0.5, which is une…
Although they are only minor constituents of the interstellar medium, halogen-containing molecules are of special interest because of their unique thermochemistry. Here, we present a theoretical study of the chemistry of interstellar molecules containing the halogen elements chlorine and fluorine. We have modeled both diffuse and dense molecular clouds, making use of updated estimates for the rates of several key chemical processes. We present predictions for the abundances of the three halogen molecules that have been detected to date in the interstellar medium: HF, CF+ and HCl. As in our pre…
Spectrally-resolved observations of three pure rotational lines of H$_2$, conducted with the EXES instrument on SOFIA toward the classic bow shock HH7, reveal systematic velocity shifts between the S(5) line of ortho-H$_2$ and the two para-H$_2$ lines [S(4) and S(6)] lying immediately above and below it on the rotational ladder. These shifts, reported here for the first time, imply that we are witnessing the conversion of para-H$_2$ to ortho-H$_2$ within a shock wave driven by an outflow from a young stellar object. The observations are in good agreement with the predictions of models for non-…
The excitation temperature T_01 derived from the relative intensities of the J = 0 (para) and J = 1 (ortho) rotational levels of H2 has been assumed to be an accurate measure of the kinetic temperature in interstellar environments. In diffuse molecular clouds, the average value of T_01 is ~70 K. However, the excitation temperature T(H3+) derived from the (J,K) = (1,1) (para) and (1,0) (ortho) rotational levels of H3+ has been observed to be ~30 K in the same types of environments. In this work, we present observations of H3+ in three additional diffuse cloud sight lines for which H2 measuremen…
We report the first detection of chloronium, H$_2$Cl$^+$, in the interstellar medium, using the HIFI instrument aboard the \emph{Herschel} Space Observatory. The $2_{12}-1_{01}$ lines of ortho-H$_2^{35}$Cl$^+$ and ortho-H$_2^{37}$Cl$^+$ are detected in absorption towards NGC~6334I, and the $1_{11}-0_{00}$ transition of para-H$_2^{35}$Cl$^+$ is detected in absorption towards NGC~6334I and Sgr~B2(S). The H$_2$Cl$^+$ column densities are compared to those of the chemically-related species HCl. The derived HCl/H$_2$Cl$^+$ column density ratios, $\sim$1--10, are within the range predicted by models…
Context. Millimetric observations have measured high degrees of molecular deuteration in several species seen around low-mass protostars. The Herschel Space Telescope, launched in 2009, is now providing new measures of the deuterium fractionation of water, the main constituent of interstellar ices. Aims. We aim at theoretically studying the formation and the deuteration of water, which is believed to be formed on interstellar grain surfaces in molecular clouds. Methods. We used our gas-grain astrochemical model GRAINOBLE, which considers the multilayer formation of interstellar ices. We varied…
New Estimate for the Cosmic Ray-Induced $\rm H_2$ Photodissociation Rate in the Interstellar Medium
Max-Planck-Institut für Extraterrestrische Physik（马克斯·普朗克地外物理研究所）；INAF – Osservatorio Astrofisico di Arcetri（意大利国家天体物理研究所 – 阿切特里天文台）；Univ Paris Est Creteil and Université Paris Cité, CNRS, LISA UMR 7583（巴黎东克雷泰伊大学和巴黎西岱大学，法国国家科学研究中心，LISA联合研究实验室）；LUX, Observatoire de Paris, PSL Research University, CNRS, Sorbonne Université（LUX，巴黎天文台，巴黎文理研究大学，法国国家科学研究中心，索邦大学）
Ammonia is one of the best tracers of cold dense cores. It is also a minor constituent of interstellar ices and, as such, one of the important nitrogen reservoirs in the protosolar nebula, together with the gas phase nitrogen, in the form of N2 and N. An important diagnostic of the various nitrogen sources and reservoirs of nitrogen in the Solar System is the 14N/15N isotopic ratio. While good data exist for the Solar System, corresponding measurements in the interstellar medium are scarce and of low quality. Following the successful detection of the singly, doubly, and triply deuterated isoto…
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…
We have used the Herschel-HIFI instrument to observe interstellar nitrogen hydrides along the sight-lines towards W49N and G10.6-0.4 in order to elucidate the production pathways leading to nitrogen-bearing species in diffuse gas. All detections show absorption by foreground material over a wide range of velocities, as well as absorption associated directly with the hot-core source itself. As in the previously published observations towards G10.6-0.4, the NH, NH2 and NH3 spectra towards W49N show strikingly similar and non-saturated absorption features. We decompose the absorption of the foreg…
Molecular clouds, the birthplaces of stars in galaxies, form dynamically from the diffuse atomic gas of the interstellar medium (ISM). The ISM is also threaded by magnetic fields which have a large impact on its dynamics. In particular, star forming regions must be magnetically supercrit- ical in order to accomodate gas clumps which can collapse under their own weight. Based on a parameter study of three dimensional magneto-hydrodyamical (MHD) simulations, we show that the long-standing problem of how such supercritical regions are generated is still an open issue.
3D tomography of the interstellar dust and gas may be useful in many respects, from the physical and chemical evolution of the ISM itself to foreground decontamination of the CMB, or various studies of the environments of specific objects. Our goal here is to bring more precise information on the distance to nearby interstellar dust and gas clouds within 250 pc. We apply the best available calibration methods to a carefully screened set of stellar Stromgren photometry data for targets possessing a Hipparcos parallax and spectral type classification. We combine the derived interstellar extincti…
Using the Herschel Space Observatory's Heterodyne Instrument for the Far-Infrared (HIFI), we have performed mapping observations of the 620.701 GHz 5(32)-4(41) transition of ortho-H2O within a roughly 1.5 x 1.5 arcmin region encompassing the Kleinmann-Low nebula in Orion, and pointed observations of that transition toward the Orion South condensation and the W49N region of high-mass star formation. Using the Effelsberg 100 m radio telescope, we obtained ancillary observations of the 22.23508 GHz 6(16)-5(23) water maser transition; in the case of Orion-KL, the 621 GHz and 22 GHz observations we…
It is well known that the dust properties of the diffuse interstellar medium exhibit variations towards different sight-lines on a large scale. We have investigated the variability of the dust characteristics on a small scale, and from cloud-to-cloud. We use low-resolution spectro-polarimetric data obtained in the context of the Large Interstellar Polarisation Survey (LIPS) towards 59 sight-lines in the Southern Hemisphere, and we fit these data using a dust model composed of silicate and carbon particles with sizes from the molecular to the sub-micrometre domain. Large (> 6 nm) silicates of p…
Chemical Evolution during Molecular Cloud Formation Triggered by an Interstellar Shock Wave: Dependence on Shock Parameters and Comparison with Molecular Absorption Lines
Neutral Interstellar Helium (NISHe) is almost unaffected at the heliospheric interface with the interstellar medium and freely enters the solar system. It provides some of the best information on the characteristics of the interstellar gas in the Local Interstellar Cloud. The Interstellar Boundary Explorer (IBEX) is the second mission to directly detect NISHe. We present a comparison between recent IBEX NISHe observations and simulations carried out using a well-tested quantitative simulation code. Simulation and observation results compare well for times when measured fluxes are dominated by …
The 2200 A bump is a major figure of interstellar extinction. Extinction curves with no bump however exist and are, with no exception, linear from the near-infrared down to 2500 A at least, often over all the visible-UV spectrum. The duality linear versus bump-like extinction curves can be used to re-investigate the relationship between the bump and the continuum of interstellar extinction, and answer questions as why do we observe two different kinds of extinction (linear or with a bump) in interstellar clouds? How are they related? How does the existence of two different extinction laws fits…
Hydride molecules lie at the base of interstellar chemistry, but the synthesis of sulfuretted hydrides is poorly understood. Motivated by new observations of the Orion Bar PDR - 1'' resolution ALMA images of SH+; IRAM 30m detections of H2S, H2S34, and H2S33; H3S+ (upper limits); and SOFIA observations of SH - we perform a systematic study of the chemistry of S-bearing hydrides. We determine their column densities using coupled excitation, radiative transfer as well as chemical formation and destruction models. We revise some of the key gas-phase reactions that lead to their chemical synthesis.…
Non-linear behavior in interstellar chemical models has been recognized for 25 years now. Different mechanisms account for the possibility of multiple fixed-points at steady state, characterized by the ionization degree of the gas. Chemical oscillations are also a natural behaviour of non-linear chemical models. We study under which conditions spontaneous sustained chemical oscillations are possible, and what kind of biffurcations lead to, or quench, the occurrence of such oscillations. Methods. The well known Ordinary Differential Equations (ODE) integrator VODE is used to explore initial con…
For decades astronomers and astrophysicists believed that only positively charged ions were worthy of relevance in drawing the networks for possible chemical reactions in the interstellar medium, as well as in modeling the physical conditions in most of astrophysical environments. Thus, molecular negative ions received minor attention until their possible existence was observationally confirmed (discovery of the first interstellar anion, C6H-), about thirty years after the first physically reasonable proposal on their actual detection was theoretically surmised by E.Herbst. In an astrophysical…
This paper tries to establish whether there are variations of the central wavelengths or the profile shapes of diffuse interstellar bands (DIBs) and whether these variations are caused by different physical parameters of translucent clouds. For this purpose we used spectra of two stars seen through two different single clouds: HD34078 (AE Aur) \& HD73882 acquired using two different instruments: the MIKE spectrograph, fed with the 6.5 m Magellan telescope at Las Campanas Observatory, and the UVES, fed with the 8 m Kueyen telescope at the Paranal observatory. The wavelength displacements of the…
We introduce a potentially powerful method for constraining or discovering a thin dark matter disk in the Milky Way. The method relies on the relationship between the midplane densities and scale heights of interstellar gas being determined by the gravitational potential, which is sensitive to the presence of a dark disk. We show how to use the interstellar gas parameters to set a bound on a dark disk and discuss the constraints suggested by the current data. However, current measurements for these parameters are discordant, with the uncertainty in the constraint being dominated by the molecul…
Recent observations of H2 and H3+ in diffuse interstellar sightlines revealed a difference in the nuclear spin excitation temperatures of the two species. This discrepancy comes as a surprise, as H3+ and H2 should undergo frequent thermalizing collisions in molecular clouds. Non-thermal behavior of the fundamental H3+ / H2 collision system at low temperatures was considered as a possible cause for the observed irregular populations. Here, we present measurements of the steady-state ortho/para ratio of H3+ in collisions with H2 molecules in a temperature-variable radiofrequency ion trap between…
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 …
Ortho-Para Chemistry of H2CO in the Protoplanetary Disk TW Hya
Université Grenoble Alpes（格勒诺布尔阿尔卑斯大学）；CNRS（法国国家科学研究中心）；Korea Astronomy and Space Science Institute（韩国天文学与空间科学研究院）；National Astronomical Observatory of Japan（日本国立天文台）；RIKEN Pioneering Research Institute（理化学研究所前沿研究机构）
Interstellar gas heating is a powerful cosmology-independent observable for exploring the parameter space of primordial black holes (PBHs) formed in the early Universe that could constitute part of the dark matter (DM). We provide a detailed analysis of the various aspects for this observable, such as PBH emission mechanisms. Using observational data from the Leo T dwarf galaxy, we constrain the PBH abundance over a broad mass-range, $M_{\rm PBH} \sim \mathcal{O}(1) M_{\odot}-10^7 M_{\odot}$, relevant for the recently detected gravitational wave signals from intermediate-mass BHs. We also cons…
The interstellar medium of the Milky Way is multi-phase, magnetized and turbulent. Turbulence in the interstellar medium produces a global cascade of random gas motions, spanning scales ranging from 100 parsecs to 1000 kilometres. Fundamental parameters of interstellar turbulence such as the sonic Mach number (the speed of sound) have been difficult to determine because observations have lacked the sensitivity and resolution to directly image the small-scale structure associated with turbulent motion. Observations of linear polarization and Faraday rotation in radio emission from the Milky Way…
