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Recent observations suggest that planets formation starts early, in protostellar disks of $\le10^5$ yrs, which are characterized by strong interactions with the environment, e.g., through accretion streamers and molecular outflows. To investigate the impact of such phenomena on disk physical and chemical properties it is key to understand what chemistry planets inherit from their natal environment. In the context of the ALMA Large Program Fifty AU STudy of the chemistry in the disk/envelope system of Solar-like protostars (FAUST), we present observations on scales from ~1500 au to ~60 au of H$_2$CO, HDCO, and D$_2$CO towards the young planet-forming disk IRS~63. H$_2$CO probes the gas in the disk as well as in a large scale streamer (~1500 au) impacting onto the South-East (SE) disk side. We detect for the first time deuterated formaldehyde, HDCO and D$_2$CO, in a planet-forming disk, and HDCO in the streamer that is feeding it. This allows us to estimate the deuterium fractionation of H$_2$CO in the disk: [HDCO]/[H$_2$CO]$\sim0.1-0.3$ and [D$_2$CO]/[H$_2$CO]$\sim0.1$. Interestingly, while HDCO follows the H$_2$CO distribution in the disk and in the streamer, the distribution of D$_2$CO is highly asymmetric, with a peak of the emission (and [D]/[H] ratio) in the SE disk side, where the streamer crashes onto the disk. In addition, D$_2$CO is detected in two spots along the blue- and red-shifted outflow. This suggests that: (i) in the disk, HDCO formation is dominated by gas-phase reactions similarly to H$_2$CO, while (ii) D$_2$CO was mainly formed on the grain mantles during the prestellar phase and/or in the disk itself, and is at present released in the gas-phase in the shocks driven by the streamer and the outflow. These findings testify on the key role of streamers in the build-up of the disk both concerning the final mass available for planet formation and its chemical composition., Comment: 12 pages, 10 figures, accepted for publication on A&A

Context. Understanding the connection between outflows, winds, accretion and disks in the inner protostellar regions is crucial for comprehending star and planet formation process. Aims. We aim to we explore the inner 300 au of the protostar IRAS 4A2 as part of the ALMA FAUST Large Program. Methods. We analysed the kinematical structures of SiO and CH$_3$OH emission with 50 au resolution. Results. The emission arises from three zones: i) a very compact and unresolved region ($<$50 au) dominated by the ice sublimation zone, at $\pm$1.5 km s$^{-1}$ with respect to vsys, traced by methanol; ii) an intermediate region (between 50 au and 150 au) traced by both SiO and CH$_3$OH, between 2 and 6 km s$^{-1}$ with respect to vsys, with an inverted velocity gradient (with respect to the large scale emission), whose origin is not clear; iii) an extended region ($>$150 au) traced by SiO, above 7 km s$^{-1}$ with respect to vsys, and dominated by the outflow. In the intermediate region we estimated a CH$_3$OH/SiO abundance ratio of about 120-400 and a SiO/H$_2$ abundance of 10$^{-8}$. We explored various possibilities to explain the origin of this region such as, rotating disk/inner envelope, jet on the plane of the sky/precessing, wide angle disk wind. Conclusions. We propose that CH$_3$OH and SiO in the inner 100 au probe the base of a wide-angle disk wind. The material accelerated in the wind crosses the plane of the sky, giving rise to the observed inverted velocity gradient, and sputtering the grain mantles and cores releasing CH$_3$OH and SiO. This is the first detection of a disk wind candidate in SiO, and the second ever in CH$_3$OH., Comment: Accepted in A&A Letters

The origin of the chemical diversity observed around low-mass protostars probably resides in the earliest history of these systems. We aim to investigate the impact of protostellar feedback on the chemistry and grain growth in the circumstellar medium of multiple stellar systems. In the context of the ALMA Large Program FAUST, we present high-resolution (50 au) observations of CH$_3$OH, H$_2$CO, and SiO and continuum emission at 1.3 mm and 3 mm towards the Corona Australis star cluster. Methanol emission reveals an arc-like structure at $\sim$1800 au from the protostellar system IRS7B along the direction perpendicular to the major axis of the disc. The arc is located at the edge of two elongated continuum structures that define a cone emerging from IRS7B. The region inside the cone is probed by H$_2$CO, while the eastern wall of the arc shows bright emission in SiO, a typical shock tracer. Taking into account the association with a previously detected radio jet imaged with JVLA at 6 cm, the molecular arc reveals for the first time a bow shock driven by IRS7B and a two-sided dust cavity opened by the mass-loss process. For each cavity wall, we derive an average H$_2$ column density of $\sim$7$\times$10$^{21}$ cm$^{-2}$, a mass of $\sim$9$\times$10$^{-3}$ M$_\odot$, and a lower limit on the dust spectral index of $1.4$. These observations provide the first evidence of a shock and a conical dust cavity opened by the jet driven by IRS7B, with important implications for the chemical enrichment and grain growth in the envelope of Solar System analogues., Comment: 12 pages, 8 figures, 3 tables. Accepted Letter in Astronomy & Astrophysics

Planetary systems such as our own are formed after a long process where matter condenses from diffuse clouds to stars, planets, asteroids, comets and residual dust, undergoing dramatic changes in physical and chemical state in less than a few million years. Several studies have shown that the chemical composition during the early formation of a Solar-type planetary system is a powerful diagnostic to track the history of the system itself. Among the approximately 270 molecules so far detected in the ISM, the so-called interstellar complex organic molecules (iCOMs) are of particular interest both because of their evolutionary diagnostic power and because they might be potential precursors of biomolecules, which are at the basis of terrestrial life. This Chapter focuses on the evolution of organic molecules during the early stages of a Solar-type planetary system, represented by the prestellar, Class 0/I and protoplanetary disk phases, and compares them with what is observed presently in Solar System comets. Our twofold goal is to review the processes at the base of organic chemistry during Solar-type star formation and, in addition, to possibly provide constraints on the early history of our own planetary system., Comment: Chapter for Protostars & Planets VII

Methanol is a ubiquitous species commonly found in the molecular interstellar medium. It is also a crucial seed species for the building-up of the chemical complexity in star forming regions. Thus, understanding how its abundance evolves during the star formation process and whether it enriches the emerging planetary system is of paramount importance. We used new data from the ALMA Large Program FAUST (Fifty AU STudy of the chemistry in the disk/envelope system of Solar-like protostars) to study the methanol line emission towards the [BHB2007] 11 protobinary system (sources A and B), where a complex structure of filaments connecting the two sources with a larger circumbinary disk has been previously detected. Twelve methanol lines have been detected with upper energies in the range [45-537] K along with one 13CH3OH transition. The methanol emission is compact and encompasses both protostars, separated by only 28 au and presents three velocity components, not spatially resolved by our observations, associated with three different spatial regions, with two of them close to 11B and the third one associated with 11A. A non-LTE radiative transfer analysis of the methanol lines concludes that the gas is hot and dense and highly enriched in methanol with an abundance as high as 1e-5. Using previous continuum data, we show that dust opacity can potentially completely absorb the methanol line emission from the two binary objects. Although we cannot firmly exclude other possibilities, we suggest that the detected hot methanol is resulting from the shocked gas from the incoming filaments streaming towards [BHB2007] 11 A and B, respectively. Higher spatial resolution observations are necessary to confirm this hypothesis., Comment: 17 pages, accepted in A&A

The study of hot corinos in Solar-like protostars has been so far mostly limited to the Class 0 phase, hampering our understanding of their origin and evolution. In addition, recent evidence suggests that planet formation starts already during Class I phase, which, therefore, represents a crucial step in the future planetary system chemical composition. Hence, the study of hot corinos in Class I protostars has become of paramount importance. Here we report the discovery of a hot corino towards the prototypical Class I protostar L1551 IRS5, obtained within the ALMA Large Program FAUST. We detected several lines from methanol and its isopotologues ($^{13}$CH$_{\rm 3}$OH and CH$_{\rm 2}$DOH), methyl formate and ethanol. Lines are bright toward the north component of the IRS5 binary system, and a possible second hot corino may be associated with the south component. The methanol lines non-LTE analysis constrains the gas temperature ($\sim$100 K), density ($\geq$1.5$\times$10$^{8}$ cm$^{-3}$), and emitting size ($\sim$10 au in radius). All CH$_{\rm 3}$OH and $^{13}$CH$_{\rm 3}$OH lines are optically thick, preventing a reliable measure of the deuteration. The methyl formate and ethanol relative abundances are compatible with those measured in Class 0 hot corinos. Thus, based on the present work, little chemical evolution from Class 0 to I hot corinos occurs., Comment: 6 pages, 2 figures

Thioformaldehyde is an abundant molecule in various regions of the interstellar medium. However, available laboratory data limit the accuracies of calculated transition frequencies in the submillimeter region, in particular for minor isotopic species. We aim to determine spectroscopic parameters of isotopologs of H2CS that are accurate enough for predictions well into the submillimeter region. We investigated the laboratory rotational spectra of numerous isotopic species in natural isotopic composition almost continuously between 110 and 377 GHz. Individual lines were studied for most species in two frequency regions between 566 and 930 GHz. Further data were obtained for the three most abundant species in the 1290-1390 GHz region. New or improved spectroscopic parameters were determined for seven isotopic species. Quantum-chemical calculations were carried out to evaluate the differences between ground state and equilibrium rotational parameters to derive semi-empirical equilibrium structural parameters. The spectroscopic parameters are accurate enough for predictions well above 1 THz with the exception of H2(13)C(34)S where the predictions should be reliable to around 700 GHz., Comment: Astron. Astrophys., in press; 12 pages

The first hydrostatic core, also called the first Larson core, is one of the first steps in low-mass star formation, as predicted by theory. With recent and future high performance telescopes, details of these first phases become accessible, and observations may confirm theory and even bring new challenges for theoreticians. In this context, we study from a theoretical point of view the chemical and physical evolution of the collapse of prestellar cores until the formation of the first Larson core, in order to better characterize this early phase in the star formation process. We couple a state-of-the-art hydrodynamical model with full gas-grain chemistry, using different assumptions on the magnetic field strength and orientation. We extract the different components of each collapsing core (i.e., the central core, the outflow, the disk, the pseudodisk, and the envelope) to highlight their specific physical and chemical characteristics. Each component often presents a specific physical history, as well as a specific chemical evolution. From some species, the components can clearly be differentiated. The different core models can also be chemically differentiated. Our simulation suggests some chemical species as tracers of the different components of a collapsing prestellar dense core, and as tracers of the magnetic field characteristics of the core. From this result, we pinpoint promising key chemical species to be observed., Comment: Accepted for publication in ApJ

We have used the Herschel-HIFI instrument to observe both nuclear spin symmetries of amidogen (NH2) towards the 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 aim is to investigate the ratio of nuclear spin types, the ortho-to-para ratio (OPR), of NH2. The excited NH2 transitions are used to construct radiative transfer models of the hot cores and surrounding envelopes in order to investigate the excitation and possible emission of the ground state rotational transitions of ortho-NH2 N_(K_a,K_c} J=1_(1,1) 3/2 - 0_(0,0) 1/2 and para-NH2 2_(1,2) 5/2 - 1_(0,1) 3/2$ used in the OPR calculations. Our best estimate of the average OPR in the envelopes lie above the high temperature limit of three for W49N, specifically 3.5 with formal errors of \pm0.1, but for W31C, W51, and G34.3+0.1 we find lower values of 2.5\pm0.1, 2.7\pm0.1, and 2.3\pm0.1, respectively. Such low values are strictly forbidden in thermodynamical equilibrium since the OPR is expected to increase above three at low temperatures. In the translucent interstellar gas towards W31C, where the excitation effects are low, we find similar values between 2.2\pm0.2 and 2.9\pm0.2. In contrast, we find an OPR of 3.4\pm0.1 in the dense and cold filament connected to W51, and also two lower limits of >4.2 and >5.0 in two other translucent gas components towards W31C and W49N. At low temperatures (T \lesssim 50 K) the OPR of H2 is <10^-1, far lower than the terrestrial laboratory normal value of three. In such a "para-enriched H2" gas, our astrochemical models can reproduce the variations of the observed OPR, both below and above the thermodynamical equilibrium value, by considering nuclear-spin gas-phase chemistry. The models suggest that values below three arise in regions with temperatures >20-25 K, depending on time, and values above three at lower temperatures., Comment: 21 pages, 23 figures. Accepted by Astronomy and Astrophysics 30 Nov 2015

Chemical models used to study the chemical composition of the gas and the ices in the interstellar medium are based on a network of chemical reactions and associated rate coefficients. These reactions and rate coefficients are partially compiled from data in the literature, when available. We present in this paper kida.uva.2014, a new updated version of the kida.uva public gas-phase network first released in 2012. In addition to a description of the many specific updates, we illustrate changes in the predicted abundances of molecules for cold dense cloud conditions as compared with the results of the previous version of our network, kida.uva.2011., Comment: Accepted for publication in ApJS on February 26th, 2015

We have observed five sulphur-bearing molecules in foreground diffuse molecular clouds lying along the sight-lines to five bright continuum sources. We have used the GREAT instrument on SOFIA to observe the 1383 GHz $^2\Pi_{3/2} J=5/2-3/2$ transitions of SH towards the star-forming regions W31C, G29.96-0.02, G34.3+0.1, W49N and W51, detecting foreground absorption towards all five sources; and the EMIR receivers on the IRAM 30m telescope at Pico Veleta to detect the H$_2$S 1(10)-1(01), CS J=2-1 and SO 3(2)-2(1) transitions. In nine foreground absorption components detected towards these sources, the inferred column densities of the four detected molecules showed relatively constant ratios, with N(SH)/N(H$_2$S) in the range 1.1 - 3.0, N(CS)/N(H$_2$S) in the range 0.32 - 0.61, and N(SO)/N(H$_2$S) in the range 0.08 - 0.30. The observed SH/H$_2$ ratios - in the range (0.5-2.6) $\times 10^{-8}$ - indicate that SH (and other sulphur-bearing molecules) account for << 1% of the gas-phase sulphur nuclei. The observed abundances of sulphur-bearing molecules, however, greatly exceed those predicted by standard models of cold diffuse molecular clouds, providing further evidence for the enhancement of endothermic reaction rates by elevated temperatures or ion-neutral drift. We have considered the observed abundance ratios in the context of shock and turbulent dissipation region (TDR) models. Using the TDR model, we find that the turbulent energy available at large scale in the diffuse ISM is sufficient to explain the observed column densities of SH and CS. Standard shock and TDR models, however, fail to reproduce the column densities of H$_2$S and SO by a factor of about 10; more elaborate shock models - in which account is taken of the velocity drift, relative to H$_2$, of SH molecules produced by the dissociative recombination of H$_3$S$^+$ - reduce this discrepancy to a factor ~ 3., Comment: 30 pages, accepted for publication in A&A

The understanding of interstellar nitrogen chemistry has improved significantly with recent results from the Herschel Space Observatory. To set even better constraints, we report here on deep searches for the NH+ ground state rotational transition J=1.5-0.5 of the ^2Pi_1/2 lower spin ladder, with fine-structure transitions at 1013 and 1019 GHz, and the para-NH2- 1_1,1-0_0,0 rotational transition at 934 GHz towards Sgr B2(M) and G10.6-0.4 using Herschel-HIFI. No clear detections of NH+ are made and the derived upper limits are <2*10^-12 and <7*10^-13 in Sgr B2(M) and G10.6-0.4, respectively. The searches are complicated by the fact that the 1013 GHz transition lies only -2.5 km/s from a CH2NH line, seen in absorption in Sgr B2(M), and that the hyperfine structure components in the 1019 GHz transition are spread over 134 km/s. Searches for the so far undetected NH2- anion turned out to be unfruitful towards G10.6-0.4, while the para-NH2- 1_1,1-0_0,0 transition was tentatively detected towards Sgr B2(M) at a velocity of 19 km/s. Assuming that the absorption occurs at the nominal source velocity of +64 km/s, the rest frequency would be 933.996 GHz, offset by 141 MHz from our estimated value. Using this feature as an upper limit, we found N(p-NH2-)<4*10^11 cm^-2. The upper limits for both species in the diffuse line-of-sight gas are less than 0.1 to 2 % of the values found for NH, NH2, and NH3 towards both sources. Chemical modelling predicts an NH+ abundance a few times lower than our present upper limits in diffuse gas and under typical Sgr B2(M) envelope conditions. The NH2- abundance is predicted to be several orders of magnitudes lower than our observed limits, hence not supporting our tentative detection. Thus, while NH2- may be very difficult to detect in interstellar space, it could, be possible to detect NH+ in regions where the ionisation rates of H2 and N are greatly enhanced., Comment: 14 pages, 19 figures, accepted for publication in Astronomy & Astrophysics 21 May, 2014

[Abridged] Ethylene oxide and its isomer acetaldehyde are important complex organic molecules because of their potential role in the formation of amino acids. Despite the fact that acetaldehyde is ubiquitous in the interstellar medium, ethylene oxide has not yet been detected in cold sources. We aim to understand the chemistry of the formation and loss of ethylene oxide in hot and cold interstellar objects (i) by including in a revised gas-grain network some recent experimental results on grain surfaces and (ii) by comparison with the chemical behaviour of its isomer, acetaldehyde. We test the code for the case of a hot core. The model allows us to predict the gaseous and solid ethylene oxide abundances during a cooling-down phase prior to star formation and during the subsequent warm-up phase. We can therefore predict at what temperatures ethylene oxide forms on grain surfaces and at what temperature it starts to desorb into the gas phase. The model reproduces the observed gaseous abundances of ethylene oxide and acetaldehyde towards high-mass star-forming regions. In addition, our results show that ethylene oxide may be present in outer and cooler regions of hot cores where its isomer has already been detected. Despite their different chemical structures, the chemistry of ethylene oxide is coupled to that of acetaldehyde, suggesting that acetaldehyde may be used as a tracer for ethylene oxide towards cold cores., Comment: 11 pages, 5 figures. Accepted by A&A

It is currently assumed that infrared dark clouds (IRDCs) represent the earliest evolutionary stages of high-mass stars ($>$ 8 M$_{\odot}$). Submillimeter and millimeter-wave studies performed over the past 15 years show that IRDCs possess a broad variety of properties, and hence a wide range of problems and questions that can be tackled. In this paper, we report an investigation of the molecular composition and chemical processes in two groups of IRDCs. Using the Mopra, APEX, and IRAM radio telescopes over the last four years, we have collected molecular line data for CO, H$_2$CO, HNCO, CH$_3$CCH, CH$_3$OH, CH$_3$CHO, CH$_3$OCHO, and CH$_3$OCH$_3$. For all of these species we estimated molecular abundances. We then undertook chemical modeling studies, concentrating on the source IRDC028.34+0.06, and compared observed and modeled abundances. This comparison showed that to reproduce observed abundances of complex organic molecules (COMs), a 0-D gas-grain model with constant physical conditions is not sufficient. We achieved greater success with the use of a warm-up model, in which warm-up from 10 K to 30 K occurs following a cold phase., Comment: accepted for publication in ApJ

The observed gas-phase molecular inventory of hot cores is believed to be significantly impacted by the products of chemistry in interstellar ices. In this study, we report the construction of a full macroscopic Monte Carlo model of both the gas-phase chemistry and the chemistry occurring in the icy mantles of interstellar grains. Our model treats icy grain mantles in a layer-by-layer manner, which incorporates laboratory data on ice desorption correctly. The ice treatment includes a distinction between a reactive ice surface and an inert bulk. The treatment also distinguishes between zeroth and first order desorption, and includes the entrapment of volatile species in more refractory ice mantles. We apply the model to the investigation of the chemistry in hot cores, in which a thick ice mantle built up during the previous cold phase of protostellar evolution undergoes surface reactions and is eventually evaporated. For the first time, the impact of a detailed multilayer approach to grain mantle formation on the warm-up chemistry is explored. The use of a multilayer ice structure has a mixed impact on the abundances of organic species formed during the warm-up phase. For example, the abundance of gaseous HCOOCH3 is lower in the multilayer model than in previous grain models that do not distinguish between layers (so-called "two phase" models). Other gaseous organic species formed in the warm-up phase are affected slightly. Finally, we find that the entrapment of volatile species in water ice can explain the two-jump behavior of H2CO previously found in observations of protostars., Comment: 50 pages, 14 figures, accepted to ApJ

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 foreground material towards W49N into different velocity components in order to investigate whether the relative abundances vary among the velocity components, and, in addition, we re-analyse the absorption lines towards G10.6-0.4 in the same manner. Abundances, with respect to molecular hydrogen, in each velocity component are estimated using CH. The analysis points to a co-existence of the nitrogen hydrides in diffuse or translucent interstellar gas with a high molecular fraction. Towards both sources, we find that NH is always at least as abundant as both o-NH2 and o-NH3, in sharp contrast to previous results for dark clouds. We find relatively constant N(NH)/N(o-NH3) and N(o-NH2)/N(o-NH3) ratios with mean values of 3.2 and 1.9 towards W49N, and 5.4 and 2.2 towards G10.6-0.4, respectively. The mean abundance of o-NH3 is ~2x10^-9 towards both sources. The nitrogen hydrides also show linear correlations with CN and HNC towards both sources, and looser correlations with CH. The upper limits on the NH+ abundance indicate column densities < 2 - 14 % of N(NH). Surprisingly low values of the ammonia ortho-to-para ratio are found in both sources, ~0.5 - 0.7 +- 0.1. This result cannot be explained by current models as we had expected to find a value of unity or higher., Comment: 35 pages, 74 figures

(Abridged) We have observed velocity resolved spectra of four ro-vibrational far-infrared transitions of C3 between the vibrational ground state and the low-energy nu2 bending mode at frequencies between 1654--1897 GHz using HIFI on board Herschel, in DR21(OH), a high mass star forming region. Several transitions of CCH and c-C3H2 have also been observed with HIFI and the IRAM 30m telescope. A gas and grain warm-up model was used to identify the primary C3 forming reactions in DR21(OH). We have detected C3 in absorption in four far-infrared transitions, P(4), P(10), Q(2) and Q(4). The continuum sources MM1 and MM2 in DR21(OH) though spatially unresolved, are sufficiently separated in velocity to be identified in the C3 spectra. All C3 transitions are detected from the embedded source MM2 and the surrounding envelope, whereas only Q(4) & P(4) are detected toward the hot core MM1. The abundance of C3 in the envelope and MM2 is \sim6x10^{-10} and \sim3x10^{-9} respectively. For CCH and c-C3H2 we only detect emission from the envelope and MM1. The observed CCH, C3, and c-C3H2 abundances are most consistent with a chemical model with n(H2)\sim5x10^{6} cm^-3 post-warm-up dust temperature, T_max =30 K and a time of \sim0.7-3 Myr. Post warm-up gas phase chemistry of CH4 released from the grain at t\sim 0.2 Myr and lasting for 1 Myr can explain the observed C3 abundance in the envelope of DR21(OH) and no mechanism involving photodestruction of PAH molecules is required. The chemistry in the envelope is similar to the warm carbon chain chemistry (WCCC) found in lukewarm corinos. The observed lower C3 abundance in MM1 as compared to MM2 and the envelope could be indicative of destruction of C3 in the more evolved MM1. The timescale for the chemistry derived for the envelope is consistent with the dynamical timescale of 2 Myr derived for DR21(OH) in other studies., Comment: 11 Pages, 6 figures, accepted for publication in A&A

We simulate the chemistry of infrared dark clouds (IRDCs) with a model in which the physical conditions are homogeneous and time-independent. The chemistry is solved as a function of time with three networks: one purely gas-phase, one that includes accretion and desorption, and one, the complete gas-grain network, that includes surface chemistry in addition. We compare our results with observed molecular abundances for two representative IRDCs -- IRDC013.90-1 and IRDC321.73-1 -- using the molecular species N$_2$H$^+$, HC$_3$N, HNC, HCO$^+$, HCN, C$_2$H, NH$_3$ and CS. IRDC013.90-1 is a cold IRDC, with a temperature below 20 K, while IRDC321.73-1 is somewhat warmer, in the range 20 - 30 K. We find that the complete gas-grain model fits the data very well, but that the goodness-of-fit is not sharply peaked at a particular temperature. Surface processes are important for the explanation of the high gas-phase abundance of N$_2$H$^+$ in IRDC321.73-1. The general success of the 0-D model in reproducing single-dish observations of our limited sample of 8 species shows that it is probably sufficient for an explanation of this type of data. To build and justify more complicated models, including spatial temperature and density structure, contraction, and heating, we require high-resolution interferometric data., Comment: accepted for publication in ApJ

We report the first detection of interstellar mercapto radicals, obtained along the sight-line to the submillimeter continuum source W49N. We have used the GREAT instrument on SOFIA to observe the 1383 GHz Doublet Pi 3/2 J = 5/2 - 3/2 lambda doublet in the upper sideband of the L1 receiver. The resultant spectrum reveals SH absorption in material local to W49N, as well as in foreground gas, unassociated with W49N, that is located along the sight-line. For the foreground material at velocities in the range 37 - 44 km/s with respect to the local standard of rest, we infer a total SH column density ~ 2.6 E+12 cm-2, corresponding to an abundance of ~ 7 E-9 relative to H2, and yielding an SH/H2S abundance ratio ~ 0.13. The observed SH/H2S abundance ratio is much smaller than that predicted by standard models for the production of SH and H2S in turbulent dissipation regions and shocks, and suggests that the endothermic neutral-neutral reaction SH + H2 -> H2S + H must be enhanced along with the ion-neutral reactions believed to produce CH+ and SH+ in diffuse molecular clouds., Comment: Accepted for publication in Astronomy and Astrophysics (SOFIA/GREAT special issue)

We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the time-dependent gas-phase chemistry of 0D and 1D interstellar sources., Comment: Accepted for publication in ApJS

An emerging theme in modern astrophysics is the connection between astronomical observations and the underlying physical phenomena that drive our cosmos. Both the mechanisms responsible for the observed astrophysical phenomena and the tools used to probe such phenomena - the radiation and particle spectra we observe - have their roots in atomic, molecular, condensed matter, plasma, nuclear and particle physics. Chemistry is implicitly included in both molecular and condensed matter physics. This connection is the theme of the present report, which provides a broad, though non-exhaustive, overview of progress in our understanding of the cosmos resulting from recent theoretical and experimental advances in what is commonly called laboratory astrophysics. This work, carried out by a diverse community of laboratory astrophysicists, is increasingly important as astrophysics transitions into an era of precise measurement and high fidelity modeling., Comment: 61 pages. 11 figures; to appear in Reports on Progress in Physics

Observations of deuterated species are useful in probing the temperature, ionization level, evolutionary stage, chemistry, and thermal history of astrophysical environments. The analysis of data from ALMA and other new telescopes requires an elaborate model of deuterium fractionation. This paper presents a publicly available chemical network with multi-deuterated species and an extended, up-to-date set of gas-phase and surface reactions. To test this network, we simulate deuterium fractionation in diverse interstellar sources. Two cases of initial abundances are considered: i) atomic except for H2 and HD, and ii) molecular from a prestellar core. We reproduce the observed D/H ratios of many deuterated molecules, and sort the species according to their sensitivity to temperature gradients and initial abundances. We find that many multiply-deuterated species produced at 10 K retain enhanced D/H ratios at temperatures $\la 100$ K. We study how recent updates to reaction rates affect calculated D/H ratios, and perform a detailed sensitivity analysis of the uncertainties of the gas-phase reaction rates in the network. We find that uncertainties are generally lower in dark cloud environments than in warm IRDCs and that uncertainties increase with the size of the molecule and number of D-atoms. A set of the most problematic reactions is presented. We list potentially observable deuterated species predicted to be abundant in low- and high-mass star-formation regions., Comment: 30 pages, 8 figures, accepted for publication in ApJS

Context: Observations of small carbon-bearing molecules such as CCH, C4H, c-C3H2, and HCO in the Horsehead Nebula have shown these species to have higher abundances towards the edge of the source than towards the center. Aims: Given the determination of a wide range of values for zeta (s-1), the total ionization rate of hydrogen atoms, and the proposal of a column-dependent zeta(N_H), where N_H is the total column of hydrogen nuclei, we desire to determine if the effects of zeta(N_H) in a single object with spatial variation can be observable. We chose the Horsehead Nebula because of its geometry and high density. Method: We model the Horsehead Nebula as a near edge-on photon dominated region (PDR), using several choices for zeta, both constant and as a function of column. The column-dependent zeta functions are determined by a Monte Carlo model of cosmic ray penetration, using a steep power-law spectrum and accounting for ionization and magnetic field effects. We consider a case with low-metal elemental abundances as well as a sulfur-rich case. Results: We show that use of a column-dependent zeta(N_H) of 5(-15) s-1 at the surface and 7.5(-16) s-1 at Av = 10 on balance improves agreement between measured and theoretical molecular abundances, compared with constant values of zeta., Comment: 12 pages, 6 figures, 5 tables, accepted in A&A

We have examined methanol emission from Orion KL with of the {\em Herschel}/HIFI instrument, and detected two methanol bands centered at 524 GHz and 1061 GHz. The 524 GHz methanol band (observed in HIFI band 1a) is dominated by the isolated $\Delta$J$=$0, K$=-4\rightarrow$-3, v$_t$$=$0 Q branch, and includes 25 E-type and 2 A-type transitions. The 1061 GHz methanol band (observed in HIFI band 4b) is dominated by the $\Delta$J$=$0, K$=7\rightarrow$6, v$_t$$=$0 Q branch transitions which are mostly blended. We have used the isolated E-type v$_t$$=$0 methanol transitions to explore the physical conditions in the molecular gas. With HIFI's high velocity resolution, the methanol emission contributed by different spatial components along the line of sight toward Orion KL (hot core, low velocity flow, and compact ridge) can be distinguished and studied separately. The isolated transitions detected in these bands cover a broad energy range (upper state energy ranging from 80 K to 900 K), which provides a unique probe of the thermal structure in each spatial component. The observations further show that the compact ridge is externally heated. These observations demonstrate the power of methanol lines as probes of the physical conditions in warm regions in close proximity to young stars., Comment: 8 pages, 9 figures, accepted for publication in Astronomy & Astrophysics

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalysed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase., Comment: Accepted for publication in Space Science Reviews

We report observations of the reactive molecular ions OH$^+$, H$_2$O$^+$, and H$_3$O$^+$ towards Orion KL with Herschel/HIFI. All three $N=1-0$ fine-structure transitions of OH$^+$ at 909, 971, and 1033GHz and both fine-structure components of the doublet {\it ortho}-H$_2$O$^+$ $1_{11}-0_{00}$ transition at 1115 and 1139GHz were detected; an upper limit was obtained for H$_3$O$^+$. OH$^+$ and H$_2$O$^+$ are observed purely in absorption, showing a narrow component at the source velocity of 9 kms$^{-1}$, and a broad blueshifted absorption similar to that reported recently for HF and {\it para}-H$_{2}^{18}$O, and attributed to the low velocity outflow of Orion KL. We estimate column densities of OH$^+$ and H$_2$O$^+$ for the 9 km s$^{-1}$ component of $9 \pm 3 \times 10^{12}$cm$^{-2}$ and $7 \pm 2 \times 10^{12}$cm$^{-2}$, and those in the outflow of $1.9 \pm 0.7 \times 10^{13}$cm$^{-2}$ and $1.0 \pm 0.3 \times 10^{13}$cm$^{-2}$. Upper limits of $2.4\times 10^{12}$cm$^{-2}$ and $8.7\times 10^{12}$cm$^{-2}$ were derived for the column densities of {\it ortho} and {\it para}-H$_3$O$^+$ from transitions near 985 and 1657GHz. The column densities of the three ions are up to an order of magnitude lower than those obtained from recent observations of W31C and W49N. The comparatively low column densities may be explained by a higher gas density despite the assumption of a very high ionization rate., Comment: 5 pages, 1 figure. Accepted to and to be published in the Herschel HIFI special issue of A\&A Letters

In contrast with numerous studies on the physical and chemical structure of low- and high-mass protostars, much less is known about their intermediate-mass counterparts, a class of objects that could help to elucidate the mechanisms of star formation on both ends of the mass range. We present the first results from a rich HIFI spectral dataset on an intermediate-mass protostar, OMC2-FIR4, obtained in the CHESS (Chemical HErschel SurveyS of star forming regions) key programme. The more than 100 methanol lines detected between 554 and 961 GHz cover a range in upper level energy of 40 to 540 K. Our physical interpretation focusses on the hot core, but likely the cold envelope and shocked regions also play a role in reality, because an analysis of the line profiles suggests the presence of multiple emission components. An upper limit of 10^-6 is placed on the methanol abundance in the hot core, using a population diagram, large-scale source model and other considerations. This value is consistent with abundances previously seen in low-mass hot cores. Furthermore, the highest energy lines at the highest frequencies display asymmetric profiles, which may arise from infall around the hot core., Comment: 2 figures, accepted for publication in the A&A Herschel-HIFI special issue

We report the detection of more than 48 velocity-resolved ground rotational state transitions of H2(16)O, H2(18)O, and H2(17)O - most for the first time - in both emission and absorption toward Orion KL using Herschel/HIFI. We show that a simple fit, constrained to match the known emission and absorption components along the line of sight, is in excellent agreement with the spectral profiles of all the water lines. Using the measured H2(18)O line fluxes, which are less affected by line opacity than their H2(16)O counterparts, and an escape probability method, the column densities of H2(18)O associated with each emission component are derived. We infer total water abundances of 7.4E-5, 1.0E-5, and 1.6E-5 for the plateau, hot core, and extended warm gas, respectively. In the case of the plateau, this value is consistent with previous measures of the Orion-KL water abundance as well as those of other molecular outflows. In the case of the hot core and extended warm gas, these values are somewhat higher than water abundances derived for other quiescent clouds, suggesting that these regions are likely experiencing enhanced water-ice sublimation from (and reduced freeze-out onto) grain surfaces due to the warmer dust in these sources., Comment: 5 pages, 2 figures

To investigate the accretion and feedback processes in massive star formation, we analyze the shapes of emission lines from hot molecular cores, whose asymmetries trace infall and expansion motions. The high-mass star forming region SgrB2(M) was observed with Herschel/HIFI (HEXOS key project) in various lines of HCN and its isotopologues, complemented by APEX data. The observations are compared to spherically symmetric, centrally heated models with density power-law gradient and different velocity fields (infall or infall+expansion), using the radiative transfer code RATRAN. The HCN line profiles are asymmetric, with the emission peak shifting from blue to red with increasing J and decreasing line opacity (HCN to H$^{13}$CN). This is most evident in the HCN 12--11 line at 1062 GHz. These line shapes are reproduced by a model whose velocity field changes from infall in the outer part to expansion in the inner part. The qualitative reproduction of the HCN lines suggests that infall dominates in the colder, outer regions, but expansion dominates in the warmer, inner regions. We are thus witnessing the onset of feedback in massive star formation, starting to reverse the infall and finally disrupting the whole molecular cloud. To obtain our result, the THz lines uniquely covered by HIFI were critically important., Comment: A&A, HIFI special issue, accepted

Observations of HDO are an important complement for studies of water, because they give strong constraints on the formation processes -- grain surfaces versus energetic process in the gas phase, e.g. in shocks. The HIFI observations of multiple transitions of HDO in Sgr~B2(M) presented here allow the determination of the HDO abundance throughout the envelope, which has not been possible before with ground-based observations only. The abundance structure has been modeled with the spherical Monte Carlo radiative transfer code RATRAN, which also takes radiative pumping by continuum emission from dust into account. The modeling reveals that the abundance of HDO rises steeply with temperature from a low abundance ($2.5\times 10^{-11}$) in the outer envelope at temperatures below 100~K through a medium abundance ($1.5\times 10^{-9}$) in the inner envelope/outer core, at temperatures between 100 and 200~K, and finally a high abundance ($3.5\times 10^{-9}$) at temperatures above 200~K in the hot core., Comment: A&A HIFI special issue, accepted

In the past decade, much progress has been made in characterising the processes leading to the enhanced deuterium fractionation observed in the ISM and in particular in the cold, dense parts of star forming regions such as protostellar envelopes. Very high molecular D/H ratios have been found for saturated molecules and ions. However, little is known about the deuterium fractionation in radicals, even though simple radicals often represent an intermediate stage in the formation of more complex, saturated molecules. The imidogen radical NH is such an intermediate species for the ammonia synthesis in the gas phase. Herschel/HIFI represents a unique opportunity to study the deuteration and formation mechanisms of such species, which are not observable from the ground. We searched here for the deuterated radical ND in order to determine the deuterium fractionation of imidogen and constrain the deuteration mechanism of this species. We observed the solar-mass Class 0 protostar IRAS16293-2422 with the heterodyne instrument HIFI as part of the Herschel key programme CHESS (Chemical HErschel Surveys of Star forming regions). The deuterated form of the imidogen radical ND was detected and securely identified with 2 hyperfine component groups of its fundamental transition in absorption against the continuum background emitted from the nascent protostar. The 3 groups of hyperfine components of its hydrogenated counterpart NH were also detected in absorption. We derive a very high deuterium fractionation with an [ND]/[NH] ratio of between 30 and 100%. The deuterium fractionation of imidogen is of the same order of magnitude as that in other molecules, which suggests that an efficient deuterium fractionation mechanism is at play. We discuss two possible formation pathways for ND, by means of either the reaction of N+ with HD, or deuteron/proton exchange with NH., Comment: Accepted; To appear in A&A Herschel/HIFI Special Issue

We present the first high spectral resolution observations of Orion KL in the frequency ranges 1573.4 - 1702.8 GHz (band 6b) and 1788.4 - 1906.8 GHz (band 7b) obtained using the HIFI instrument on board the Herschel Space Observatory. We characterize the main emission lines found in the spectrum, which primarily arise from a range of components associated with Orion KL including the hot core, but also see widespread emission from components associated with molecular outflows traced by H2O, SO2, and OH. We find that the density of observed emission lines is significantly diminished in these bands compared to lower frequency Herschel/HIFI bands., Comment: Accepted for publication in the Herschel HIFI special issue of Astronomy and Astrophysics Letters, 5 pages, 3 figures

Despite the low elemental deuterium abundance in the Galaxy, enhanced molecular D/H ratios have been found in the environments of low-mass star forming regions, and in particular the Class 0 protostar IRAS 16293-2422. The CHESS (Chemical HErschel Surveys of Star forming regions) Key Program aims at studying the molecular complexity of the interstellar medium. The high sensitivity and spectral resolution of the HIFI instrument provide a unique opportunity to observe the fundamental 1,1,1 - 0,0,0 transition of the ortho-D2O molecule, inaccessible from the ground, and to determine the ortho-to-para D2O ratio. We have detected the fundamental transition of the ortho-D2O molecule at 607.35 GHz towards IRAS 16293-2422. The line is seen in absorption with a line opacity of 0.62 +/- 0.11 (1 sigma). From the previous ground-based observations of the fundamental 1,1,0 - 1,0,1 transition of para-D2O seen in absorption at 316.80 GHz we estimate a line opacity of 0.26 +/- 0.05 (1 sigma). We show that the observed absorption is caused by the cold gas in the envelope of the protostar. Using these new observations, we estimate for the first time the ortho to para D2O ratio to be lower than 2.6 at a 3 sigma level of uncertainty, to be compared with the thermal equilibrium value of 2:1., Comment: 5 pages, 5 figures, accepted the A&A HIFI Special Issue as a letter

We present observations of twelve rotational transitions of H2O-16, H2O-18, and H2O-17 toward the massive star-forming region NGC 6334 I, carried out with Herschel/HIFI as part of the guaranteed time key program Chemical HErschel Surveys of Star forming regions (CHESS). We analyze these observations to obtain insights into physical processes in this region. We identify three main gas components (hot core, cold foreground, and outflow) in NGC 6334 I and derive the physical conditions in these components. The hot core, identified by the emission in highly excited lines, shows a high excitation temperature of 200 K, whereas water in the foreground component is predominantly in the ortho- and para- ground states. The abundance of water varies between 4 10^-5 (outflow) and 10^-8 (cold foreground gas). This variation is most likely due to the freeze-out of water molecules onto dust grains. The H2O-18/H2O-17 abundance ratio is 3.2, which is consistent with the O-18/O-17 ratio determined from CO isotopologues. The ortho/para ratio in water appears to be relatively low 1.6(1) in the cold, quiescent gas, but close to the equilibrium value of three in the warmer outflow material (2.5(0.8))., Comment: 7 pages, 3 figures, accepted by A&A

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 spectra show similar, non-saturated, absorption features, which we attribute to diffuse molecular gas. Total column densities over the velocity range 11-54 km/s are estimated. The similar profiles suggest fairly uniform abundances relative to hydrogen, approximately 6*10^-9, 3*10^-9, and 3*10^-9 for NH, NH2, and NH3, respectively. These abundances are discussed with reference to models of gas-phase and surface chemistry., Comment: 5 pages, 3 figures, 2 online pages with 2 figures. Accepted for publication in A&A July 6 (Herschel/HIFI special issue)

We present initial results from the Herschel GT key program: Herschel observations of EXtra-Ordinary Sources (HEXOS) and outline the promise and potential of spectral surveys with Herschel/HIFI. The HIFI instrument offers unprecedented sensitivity, as well as continuous spectral coverage across the gaps imposed by the atmosphere, opening up a largely unexplored wavelength regime to high-resolution spectroscopy. We show the spectrum of Orion KL between 480 and 560 GHz and from 1.06 to 1.115 THz. From these data, we confirm that HIFI separately measures the dust continuum and spectrally resolves emission lines in Orion KL. Based on this capability we demonstrate that the line contribution to the broad-band continuum in this molecule-rich source is ~20-40% below 1 THz and declines to a few percent at higher frequencies. We also tentatively identify multiple transitions of HD18O in the spectra. The first detection of this rare isotopologue in the interstellar medium suggests that HDO emission is optically thick in the Orion hot core with HDO/H2O ~ 0.02. We discuss the implications of this detection for the water D/H ratio in hot cores., Comment: 6 pages, 5 figures, accepted and to be published in Herschel HIFI special issue of A&A Letters

We discuss the detection of absorption by interstellar hydrogen fluoride (HF) along the sight line to the submillimeter continuum sources W49N and W51. We have used Herschel's HIFI instrument in dual beam switch mode to observe the 1232.4762 GHz J = 1 - 0 HF transition in the upper sideband of the band 5a receiver. We detected foreground absorption by HF toward both sources over a wide range of velocities. Optically thin absorption components were detected on both sight lines, allowing us to measure - as opposed to obtain a lower limit on - the column density of HF for the first time. As in previous observations of HF toward the source G10.6-0.4, the derived HF column density is typically comparable to that of water vapor, even though the elemental abundance of oxygen is greater than that of fluorine by four orders of magnitude. We used the rather uncertain N(CH)-N(H2) relationship derived previously toward diffuse molecular clouds to infer the molecular hydrogen column density in the clouds exhibiting HF absorption. Within the uncertainties, we find that the abundance of HF with respect to H2 is consistent with the theoretical prediction that HF is the main reservoir of gas-phase fluorine for these clouds. Thus, hydrogen fluoride has the potential to become an excellent tracer of molecular hydrogen, and provides a sensitive probe of clouds of small H2 column density. Indeed, the observations of hydrogen fluoride reported here reveal the presence of a low column density diffuse molecular cloud along the W51 sight line, at an LSR velocity of ~ 24kms-1, that had not been identified in molecular absorption line studies prior to the launch of Herschel., Comment: 4 pages, 3 figures, A&A Letter special issue, accepted on 07/13/2010

We report a detection of the fundamental rotational transition of hydrogen fluoride in absorption towards Orion KL using Herschel/HIFI. After the removal of contaminating features associated with common molecules ("weeds"), the HF spectrum shows a P-Cygni profile, with weak redshifted emission and strong blue-shifted absorption, associated with the low-velocity molecular outflow. We derive an estimate of 2.9 x 10^13 cm^-2 for the HF column density responsible for the broad absorption component. Using our best estimate of the H2 column density within the low-velocity molecular outflow, we obtain a lower limit of ~1.6 x 10^-10 for the HF abundance relative to hydrogen nuclei, corresponding to 0.6% of the solar abundance of fluorine. This value is close to that inferred from previous ISO observations of HF J=2--1 absorption towards Sgr B2, but is in sharp contrast to the lower limit of 6 x 10^-9 derived by Neufeld et al. (2010) for cold, foreground clouds on the line of sight towards G10.6-0.4., Comment: 5 pages, 3 figures, paper to be published in the Herschel special issue of A&A letters

We have observed CH absorption lines ($J=3/2, N=1 \leftarrow J=1/2, N=1$) against the continuum source Sgr~B2(M) using the \textit{Herschel}/HIFI instrument. With the high spectral resolution and wide velocity coverage provided by HIFI, 31 CH absorption features with different radial velocities and line widths are detected and identified. The narrower line width and lower column density clouds show `spiral arm' cloud characteristics, while the absorption component with the broadest line width and highest column density corresponds to the gas from the Sgr~B2 envelope. The observations show that each `spiral arm' harbors multiple velocity components, indicating that the clouds are not uniform and that they have internal structure. This line-of-sight through almost the entire Galaxy offers unique possibilities to study the basic chemistry of simple molecules in diffuse clouds, as a variety of different cloud classes are sampled simultaneously. We find that the linear relationship between CH and H$_2$ column densities found at lower $A_V$ by UV observations does not continue into the range of higher visual extinction. There, the curve flattens, which probably means that CH is depleted in the denser cores of these clouds., Comment: Accepted for publication in A&A, HIFI Special Issue

In contrast to extensively studied dense star-forming cores, little is known about diffuse gas surrounding star-forming regions. We study molecular gas in the high-mass star-forming region NGC6334I, which contains diffuse, quiescent components that are inconspicuous in widely used molecular tracers such as CO. We present Herschel/HIFI observations of CH toward NGC6334I observed as part of the CHESS key program. HIFI resolves the hyperfine components of its J=3/2-1/2 transition, observed in both emission and absorption. The CH emission appears close to the systemic velocity of NGC6334I, while its measured linewidth of 3 km/s is smaller than previously observed in dense gas tracers such as NH3 and SiO. The CH abundance in the hot core is 7 10^-11, two to three orders of magnitude lower than in diffuse clouds. While other studies find distinct outflows in, e.g., CO and H2O toward NGC6334I, we do not detect outflow signatures in CH. To explain the absorption signatures, at least two absorbing components are needed at -3.0 and +6.5 km/s with N(CH)=7 10^13 and 3 10^13 cm^-2. Two additional absorbing clouds are found at +8.0 and 0.0 km/s, both with N(CH)=2 10^13 cm^-2. Turbulent linewidths for the four absorption components vary between 1.5 and 5.0 km/s in FWHM. We constrain physical properties of our CH clouds by matching our CH absorbers with other absorption signatures. In the hot core, molecules such as H2O and CO trace gas that is heated and dynamically influenced by outflow activity, whereas CH traces more quiescent material. The four CH absorbers have column densities and turbulent properties consistent with diffuse clouds: two are located near NGC6334, and two are unrelated foreground clouds. Local density and dynamical effects influence the chemical composition of physical components of NGC6334, causing some components to be seen in CH but not in other tracers, and vice versa., Comment: Accepted by A&A Letters; 5 pages, 1 figure; v2: minor textual and typographical changes

We present Herschel/HIFI observations of the fundamental rotational transitions of ortho- and para-H$_2^{16}$O and H$_2^{18}$O in absorption towards Sagittarius~B2(M) and W31C. The ortho/para ratio in water in the foreground clouds on the line of sight towards these bright continuum sources is generally consistent with the statistical high-temperature ratio of 3, within the observational uncertainties. However, somewhat unexpectedly, we derive a low ortho/para ratio of $2.35 \pm 0.35$, corresponding to a spin temperature of $\sim$27~K, towards Sagittarius~B2(M) at velocities of the expanding molecular ring. Water molecules in this region appear to have formed with, or relaxed to, an ortho/para ratio close to the value corresponding to the local temperature of the gas and dust., Comment: Accepted for publication in A&A, HIFI Special Issue; 5 pages, 3 figures

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$1--10, are within the range predicted by models of diffuse and dense Photon Dominated Regions (PDRs). However, the observed H$_2$Cl$^+$ column densities, in excess of $10^{13}$~cm$^{-2}$, are significantly higher than the model predictions. Our observations demonstrate the outstanding spectroscopic capabilities of HIFI for detecting new interstellar molecules and providing key constraints for astrochemical models., Comment: Accepted for publication in A&A, HIFI Special Issue; 4 pages, 2 figures, 1 table

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 observed OH+ arises in clouds of small molecular fraction, in the 2 - 8% range. This conclusion is confirmed by the distribution of OH+ and H2O+ in Doppler velocity space, which is similar to that of atomic hydrogen, as observed by means of 21 cm absorption measurements, and dissimilar from that typical of other molecular tracers. The observed OH+/H abundance ratio of a few E-8 suggests a cosmic ray ionization rate for atomic hydrogen of (0.6 - 2.4) E-16 s-1, in good agreement with estimates inferred previously for diffuse clouds in the Galactic disk from observations of interstellar H3+ and other species., Comment: Accepted for publication in A&A Letters

H2O+ has been observed in its ortho- and para- states toward the massive star forming core Sgr B2(M), located close to the Galactic center. The observations show absorption in all spiral arm clouds between the Sun and Sgr B2. The average o/p ratio of H2O+ in most velocity intervals is 4.8, which corresponds to a nuclear spin temperature of 21 K. The relationship of this spin temperature to the formation temperature and current physical temperature of the gas hosting H2O+ is discussed, but no firm conclusion is reached. In the velocity interval 0 to 60 km/s, an ortho/para ratio of below unity is found, but if this is due to an artifact of contamination by other species or real is not clear., Comment: A&A, HIFI special issue, accepted

The outflow driven by the low-mass class 0 protostar L1157 is the prototype of the so-called chemically active outflows. The bright bowshock B1 in the southern outflow lobe is a privileged testbed of magneto-hydrodynamical (MHD) shock models, for which dynamical and chemical processes are strongly interdependent. We present the first results of the unbiased spectral survey of the L1157-B1 bowshock, obtained in the framework of the key program "Chemical Herschel Surveys of Star Forming Regions" (CHESS). The main aim is to trace the warm and chemically enriched gas and to infer the excitation conditions in the shock region. The CO 5-4 and H2O lines have been detected at high-spectral resolution in the unbiased spectral survey of the HIFI-Band 1b spectral window (555-636 GHz), presented by Codella et al. in this volume. Complementary ground-based observations in the submm window help establish the origin of the emission detected in the main-beam of HIFI, and the physical conditions in the shock.}{Both lines exhibit broad wings, which extend to velocities much higher than reported up to now. We find that the molecular emission arises from two regions with distinct physical conditions: an extended, warm (100K), dense (3e5 cm-3) component at low-velocity, which dominates the water line flux in Band~1; a secondary component in a small region of B1 (a few arcsec) associated with high-velocity, hot (> 400 K) gas of moderate density ((1.0-3.0)e4 cm-3), which appears to dominate the flux of the water line at 179mu observed with PACS. The water abundance is enhanced by two orders of magnitude between the low- and the high-velocity component, from 8e-7 up to 8e-5. The properties of the high-velocity component agree well with the predictions of steady-state C-shock models., Comment: Accepted for Publication in Astronomy and Astrophysics (Herschel Special Issue)

We identify a prominent absorption feature at 1115 GHz, detected in first HIFI spectra towards high-mass star-forming regions, and interpret its astrophysical origin. The characteristic hyperfine pattern of the H2O+ ground-state rotational transition, and the lack of other known low-energy transitions in this frequency range, identifies the feature as H2O+ absorption against the dust continuum background and allows us to derive the velocity profile of the absorbing gas. By comparing this velocity profile with velocity profiles of other tracers in the DR21 star-forming region, we constrain the frequency of the transition and the conditions for its formation. In DR21, the velocity distribution of H2O+ matches that of the [CII] line at 158\mu\m and of OH cm-wave absorption, both stemming from the hot and dense clump surfaces facing the HII-region and dynamically affected by the blister outflow. Diffuse foreground gas dominates the absorption towards Sgr B2. The integrated intensity of the absorption line allows us to derive lower limits to the H2O+ column density of 7.2e12 cm^-2 in NGC 6334, 2.3e13 cm^-2 in DR21, and 1.1e15 cm^-2 in Sgr B2., Comment: Accepted for publication in A&A

We report the detection of strong absorption by interstellar hydrogen fluoride along the sight-line to the submillimeter continuum source G10.6-0.4 (W31C). We have used Herschel's HIFI instrument, in dual beam switch mode, to observe the 1232.4763 GHz J=1-0 HF transition in the upper sideband of the Band 5a receiver. The resultant spectrum shows weak HF emission from G10.6-0.4 at LSR velocities in the range -10 to -3 km/s, accompanied by strong absorption by foreground material at LSR velocities in the range 15 to 50 km/s. The spectrum is similar to that of the 1113.3430 GHz 1(11)-0(00) transition of para-water, although at some frequencies the HF (hydrogen fluoride) optical depth clearly exceeds that of para-H2O. The optically-thick HF absorption that we have observed places a conservative lower limit of 1.6E+14 cm-2 on the HF column density along the sight-line to G10.6-0.4. Our lower limit on the HF abundance, 6E-9 relative to hydrogen nuclei, implies that hydrogen fluoride accounts for between ~ 30 and 100% of the fluorine nuclei in the gas phase along this sight-line. This observation corroborates theoretical predictions that - because the unique thermochemistry of fluorine permits the exothermic reaction of F atoms with molecular hydrogen - HF will be the dominant reservoir of interstellar fluorine under a wide range of conditions., Comment: Accepted for publication in Astronomy and Astrophysics (Herschel special issue). This revised version corrects a typographic error in the HTML abstract, in which the lower limit on the HF abundance (should be 6E-9) was previously misstated. The abstract in the PDF version is correct and the latter has not been modified

Because of new telescopes that will dramatically improve our knowledge of the interstellar medium, chemical models will have to be used to simulate the chemistry of many regions with diverse properties. To make these models more robust, it is important to understand their sensitivity to a variety of parameters. In this article, we report a study of the sensitivity of a chemical model of a cold dense core, with homogeneous and time-independent physical conditions, to variations in the following parameters: initial chemical inventory, gas temperature and density, cosmic-ray ionization rate, chemical reaction rate coefficients, and elemental abundances. From the results of the parameter variations, we can quantify the sensitivity of the model to each parameter as a function of time. Our results can be used in principle with observations to constrain some parameters for different cold clouds. We also attempted to use the Monte Carlo approach with all parameters varied collectively. Within the parameter ranges studied, the most critical parameters turn out to be the reaction rate coefficients at times up to 4e5 yr and elemental abundances at later times. At typical times of best agreement with observation, models are sensitive to both of these parameters. The models are less sensitive to other parameters such as the gas density and temperature. The improvement of models will require that the uncertainties in rate coefficients of important reactions be reduced. As the chemistry becomes better understood and more robust, it should be possible to use model sensitivities concerning other parameters, such as the elemental abundances and the cosmic ray ionization rate, to yield detailed information on cloud properties and history. Nevertheless, at the current stage, we cannot determine the best values of all the parameters simultaneously based on purely observational constraints., Comment: Accepted for publication in Astronomy & Astrophysics