M. Agúndez

Laboratory and Astronomical Detection of the Negative Molecular Ion C3N

The negative molecular ion C3N− has been detected at millimeter wavelengths in a low-pressure laboratory discharge, and then with frequencies derived from the laboratory data in the molecular envelope of IRC+10216. Spectroscopic constants derived from laboratory measurements of 12 transitions between 97 and 378 GHz allow the rotational spectrum to be calculated well into the submillimeter-wave band to 0.03 km s−1 or better in equivalent radial velocity. Four transitions of C3N− were detected in IRC+10216 with the IRAM 30 m telescope at precisely the frequencies calculated from the laboratory measurements. The column density of C3N− is 0.5% that of C3N, or approximately 20 times greater than that of C4H− relative to C4H. The C3N− abundance in IRC+10216 is compared with a chemical model calculation by Petrie & Herbst. An upper limit in TMC-1 for C3N− relative to C3N (<0.8%) and a limit for C4H− relative to C4H (<0.004%) that is 5 times lower than that found in IRC+10216, were obtained from observations with the NRAO 100 m Green Bank Telescope (GBT). The fairly high concentration of C3N− achieved in the laboratory implies that other molecular anions containing the CN group may be within reach.

Reaction networks for interstellar chemical modelling: Improvements and challenges.

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 key 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-catalyzed 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.

Detection of C5N− and Vibrationally Excited C6H in IRC +10216*

We report the detection in the envelope of the C-rich star IRC +10216 of four series of lines with harmonically related frequencies: B1389, B1390, B1394 and B1401. The four series must arise from linear molecules with mass and size close to those of C6H and C5N. Three of the series have half-integer rotational quantum numbers; we assign them to the 2Delta and 2Sigma vibronic states of C6H in its lowest (v_11) bending mode. The fourth series, B1389, has integer J with no evidence of fine or hyperfine structure; it has a rotational constant of 1388.860(2) MHz and a centrifugal distortion constant of 33(1) Hz; it is almost certainly the C5N- anion.

Astronomical identification of CN-, the smallest observed molecular anion

We present the first astronomical detection of a diatomic negative ion, the cyanide anion CN-, as well as quantum mechanical calculations of the excitation of this anion through collisions with para-H2. CN- is identified through the observation of the J = 2-1 and J = 3-2 rotational transitions in the C-star envelope IRC +10216 with the IRAM 30-m telescope. The U-shaped line profiles indicate that CN-, like the large anion C6H-, is formed in the outer regions of the envelope. Chemical and excitation model calculations suggest that this species forms from the reaction of large carbon anions with N atoms, rather than from the radiative attachment of an electron to CN, as is the case for large molecular anions. The unexpectedly large abundance derived for CN-, 0.25 % relative to CN, makes likely its detection in other astronomical sources. A parallel search for the small anion C2H- remains so far unconclusive, despite the previous tentative identification of the J = 1-0 rotational transition. The abundance of C2H- in IRC +10216 is found to be vanishingly small, < 0.0014 % relative to C2H.

Oxygen Chemistry in the Circumstellar Envelope of the Carbon-Rich Star IRC +10216

In this paper we study the oxygen chemistry in the C-rich circumstellar shells of IRC +10216. The recent discoveries of oxygen-bearing species (water, hydroxyl radical, and formaldehyde) toward this source challenge our current understanding of the chemistry in C-rich circumstellar envelopes. The presence of icy comets surrounding the star or catalysis on iron grain surfaces have been invoked to explain the presence of such unexpected species. This detailed study aims at evaluating the chances of producing O-bearing species in the C-rich circumstellar envelope only by gas-phase chemical reactions. For the hot inner envelope we show that although most of the oxygen is locked in CO near the photosphere (as expected for a C/O ratio greater than 1), for radial distances larger than ~15 stellar radii, species such as H2O and CO2 have a large abundance under the assumption of thermochemical equilibrium. It is also shown how non-LTE chemistry makes the CO ? H2O, CO2 transformation predicted in LTE very difficult. Concerning the chemistry in the colder, outer envelope, we show that formaldehyde can be formed through gas-phase reactions. However, in order to form water vapor, it is necessary to include a radiative association between atomic oxygen and molecular hydrogen with quite a high rate constant. The chemical models explain the presence of HCO+ and predict the existence of SO and H2CS (which has been detected in a 3 mm line survey to be published). We have modeled the line profiles of H2CO, H2O, HCO+, SO, and H2CS using a nonlocal radiative transfer model and the abundance profiles predicted by our chemical model. The results have been compared to the observations and discussed.

A chemical model for the atmosphere of hot Jupiters

Our purpose is to release a chemical network, and the associated rate coefficients, developed for the temperature and pressure range relevant to hot Jupiters atmospheres. Using this network, we study the vertical atmospheric composition of the two hot Jupiters (HD209458b, HD189733b) with a model that includes photolyses and vertical mixing and we produce synthetic spectra. The chemical scheme is derived from applied combustion models that have been methodically validated over a range of temperatures and pressures typical of the atmospheric layers influencing the observations of hot Jupiters. We compare the predictions obtained from this scheme with equilibrium calculations, with different schemes available in the literature that contain N-bearing species and with previously published photochemical models. Compared to other chemical schemes that were not subjected to the same systematic validation, we find significant differences whenever non-equilibrium processes take place. The deviations from the equilibrium, and thus the sensitivity to the network, are more important for HD189733b, as we assume a cooler atmosphere than for HD209458b. We found that the abundances of NH3 and HCN can vary by two orders of magnitude depending on the network, demonstrating the importance of comprehensive experimental validation. A spectral feature of NH3 at 10.5

The chemistry of vibrationally excited H2 in the interstellar medium

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Search for anions in molecular sources : C4H-detection in L1527

m is sensitive to these abundance variations and thus to the chemical scheme. Due to the influence of the kinetics, we recommend the use of a validated scheme to model the chemistry of exoplanet atmospheres. Our network is robust for temperatures within 300-2500K and pressures from 10mbar up to a few hundreds of bars, for species made of C,H,O,N. It is validated for species up to 2 carbon atoms and for the main nitrogen species.

Chemistry of Dark Clouds: Databases, Networks, and Models

The internal energy available in vibrationally excited H2 molecules can be used to overcome or diminish the activation barrier of various chemical reactions of interest for molecular astrophysics. In this paper, we investigate in detail the impact on the chemical composition of interstellar clouds of the reactions of vibrationally excited H2 with C+, He+, O, OH, and CN, based on the available chemical kinetics data. It is found that the reaction of H2 (v>0) and C+ has a profound impact on the abundances of some molecules, especially CH+, which is a direct product and is readily formed in astronomical regions with fractional abundances of vibrationally excited H2, relative to the ground state H2, in excess of ~10–6, independently of whether the gas is hot or not. The effects of these reactions on the chemical composition of the diffuse clouds ζOph and HD 34078, the dense photon-dominated region (PDR) Orion Bar, the planetary nebula NGC 7027, and the circumstellar disk around the B9 star HD 176386 are investigated through PDR models. We find that formation of CH+ is especially favored in dense and highly FUV illuminated regions such as the Orion Bar and the planetary nebula NGC 7027, where column densities in excess of 1013 cm–2 are predicted. In diffuse clouds, however, this mechanism is found to be not efficient enough to form CH+ with a column density close to the values derived from astronomical observations.

Warm water vapour in the sooty outflow from a luminous carbon star

Based on observations carried out with the IRAM 30 m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).-- Accepted for publication in Astronomy & Astrophysics Letters.