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We have observed 29 transitions corresponding to 12 distinct species and 7 additional isotopologs toward the deeply embedded Class 0 young stellar object Ser-emb 1 with the Atacama Large Millimeter Array at 1 mm. The detected species include CH3OH and two complex organic molecules, CH3OCH3 and CH3OCHO. The emission of CH3OH and the two COMs is compact, and the CH3OH rotational temperature is 261 (46) K, implying that Ser-emb 1 hosts a hot corino. The derived CH3OH, CH3OCH3 and CH3OCHO column densities are at least 1.2 (0.4)E17 cm-2, 9.2 (3.8)E16 cm-2, and 9.1 (3.6)E16 cm-2, respectively, comparable to the values found for other Class 0 hot corinos. In addition, we observe evidence of rotation at compact scales: two of the more strongly detected lines, corresponding to C18O and H2CO present spatially resolved red- and blue-shifted compact emission orthogonal to the direction of a jet and outflow traced by CO, SiO, and several other molecules. The spatial coincidence of the hot corino emission and a possible disk in a compact region around the central protostar suggests that these structures may be physically and/or chemically related.

Ortho-to-para (o/p) ratios of species like water, ammonia and formaldehyde (H2CO) are believed to encode information about the formation history of the molecule. Measurements of o/p ratios in protoplanetary disks could thus be used to constrain their physical and chemical histories. We present the first measurement of the H2CO o/p ratio in a protoplanetary disk, using three ortho and two para lines observed with the Sub-millimeter Array (SMA) combined with one highly resolved measurement of a single H2CO line with ALMA toward the disk around Herbig Ae star HD 163296. We find a disk-averaged H2CO o/p ratio of 1.8-2.8 (depending on the assumed disk structure), corresponding to a spin temperature of 11-22 K. We also derive a rotational temperature of 24 K from the flux ratio of the three ortho lines. The observed spatial distribution, as seen by ALMA, as well as the rotational temperature and the o/p ratio, at the large scales the SMA is most sensitive to, are consistent with a low-temperature formation pathway, most likely grain surface chemistry, of H2CO in this disk., Comment: 9 pages, 7 figures, 4 tables; Accepted for publication in ApJ

We have used the Submillimeter Array to image, at ~1" resolution, C2H(3-2) emission from the molecule-rich circumstellar disks orbiting the nearby, classical T Tauri star systems TW Hya and V4046 Sgr. The SMA imaging reveals that the C2H emission exhibits a ring-like morphology within each disk, the inner hole radius of the C2H ring within the V4046 Sgr disk (~70 AU) is somewhat larger than than of its counterpart within the TW Hya disk (~45 AU). We suggest that, in each case, the C2H emission likely traces irradiation of the tenuous surface layers of the outer disks by high-energy photons from the central stars., Comment: 2 pages, 2 figures, to appear in "Young Stars and Planets Near the Sun", Proceedings of IAU Symposium No. 314 (Cambridge University Press), J.H. Kastner, B. Stelzer, S.A. Metchev, eds

Small hydrocarbons, such as C2H, C3H and C3H2 are more abundant in photo-dissociation regions (PDRs) than expected based on gas-phase chemical models. To explore the hydrocarbon chemistry further, we observed a key intermediate species, the hydrocarbon ion l-C3H+, in the Horsehead PDR with the Plateau de Bure Interferometer at high-angular resolution (6''). We compare with previous observations of C2H and c-C3H2 at similar angular resolution and new gas-phase chemical model predictions to constrain the dominant formation mechanisms of small hydrocarbons in low-UV flux PDRs. We find that, at the peak of the HCO emission (PDR position), the measured l-C3H+, C2H and c-C3H2 abundances are consistent with current gas-phase model predictions. However, in the first PDR layers, at the 7.7 mum PAH band emission peak, which are more exposed to the radiation field and where the density is lower, the C2H and c-C3H2 abundances are underestimated by an order of magnitude. At this position, the l-C3H+ abundance is also underpredicted by the model but only by a factor of a few. In addition, contrary to the model predictions, l-C3H+ peaks further out in the PDR than the other hydrocarbons, C2H and c-C3H2. This cannot be explained by an excitation effect. Current gas-phase photochemical models thus cannot explain the observed abundances of hydrocarbons, in particular in the first PDR layers. Our observations are consistent with a top-down hydrocarbon chemistry, in which large polyatomic molecules or small carbonaceous grains are photo-destroyed into smaller hydrocarbon molecules/precursors., Comment: 6 pages, 3 figures, 2 tables. Accepted for publication in ApJL

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

(Abridged) Gas-phase complex organic molecules are commonly detected in the warm inner regions of protostellar envelopes. Recent models show that photochemistry in ices followed by desorption may explain the observed abundances. This study aims to experimentally quantify the broad-band UV-induced production rates of complex organics in CH3OH-rich ices at 20-70 K under ultra-high vacuum conditions. The reaction products are mainly identified by RAIRS and TPD experiments. Complex organics are readily formed in all experiments, both during irradiation and during a slow warm-up of the ices to 200 K after the UV lamp is turned off. The relative abundances of photoproducts depend on the UV fluence, the ice temperature, and whether pure CH3OH ice or CH3OH:CH4/CO ice mixtures are used. C2H6, CH3CHO, CH3CH2OH, CH3OCH3, HCOOCH3, HOCH2CHO and (CH2OH)2 are all detected in at least one experiment. The derived product-formation yields and their dependences on different experimental parameters, such as the initial ice composition, are used to estimate the CH3OH photodissociation branching ratios in ice and the relative diffusion barriers of the formed radicals. The experiments show that ice photochemistry in CH3OH ices is efficient enough to explain the observed abundances of complex organics around protostars and that ratios of complex molecules can be used to constrain their formation pathway., Comment: Accepted for publication in A&A. 65 pages including appendices

With the goal to study the physical and chemical evolution of ices in solar-mass systems, a spectral survey is conducted of a sample of 41 low luminosity YSOs using 3-38 um Spitzer and ground-based spectra. The long-known 6.0 and 6.85 um bands are detected toward all sources, with the Class 0-type YSOs showing the deepest bands ever observed. In almost all sources the 6.0 um band is deeper than expected from the bending mode of pure solid H2O. The depth and shape variations of the remaining 5-7 um absorption indicate that it consists of 5 independent components, which, by comparison to laboratory studies, must be from at least 8 different carriers. Simple species are responsible for much of the absorption in the 5-7 um region, at abundances of 1-30% for CH3OH, 3-8% for NH3, 1-5% for HCOOH, ~6% for H2CO, and ~0.3% for HCOO- with respect to solid H2O. The 6.85 um band likely consists of one or two carriers, of which one is less volatile than H2O because its abundance relative to H2O is enhanced at lower H2O/tau_9.7 ratios. It does not survive in the diffuse interstellar medium (ISM), however. The similarity of the 6.85 um bands for YSOs and background stars indicates that its carrier(s) must be formed early in the molecular cloud evolution. If an NH4+ salt is the carrier its abundance with respect to solid H2O is typically 7%, and low temperature acid-base chemistry or cosmic ray induced reactions must have been involved in its formation. Possible origins are discussed for the carrier of an enigmatic, very broad absorption between 5 and 8 um. Finally, all the phenomena observed for ices toward massive YSOs are also observed toward low mass YSOs, indicating that processing of the ices by internal ultraviolet radiation fields is a minor factor in the early chemical evolution of the ices. [abridged], Comment: Accepted for publication in ApJ. 22 pages, 18 b&w figures

We present Temperature Programmed Desorption (TPD) experiments of CO and N2 ices in pure, layered and mixed morphologies at various ice "thicknesses" and abundance ratios as well as simultaneously taken Reflection Absorption Infrared Spectra (RAIRS) of CO. A kinetic model has been developed to constrain the binding energies of CO and N2 in both pure and mixed environments and to derive the kinetics for desorption, mixing and segregation. For mixed ices N2 desorption occurs in a single step whereas for layered ices it proceeds in two steps, one corresponding to N2 desorption from a pure N2 ice environment and one corresponding to desorption from a mixed ice environment. The latter is dominant for astrophysically relevant ice "thicknesses". The ratio of the binding energies, Rbe, for pure N2 and CO is found to be 0.936 +/- 0.03, and to be close to 1 for mixed ice fractions. The model is applied to astrophysically relevant conditions for cold pre-stellar cores and for protostars which start to heat their surroundings. The importance of treating CO desorption with zeroth rather than first order kinetics is shown. The experiments also provide lower limits of 0.87 +/- 0.05 for the sticking probabilities of CO-CO, N2-CO and N2-N2 ices at 14 K. The combined results from the desorption experiments, the kinetic model, and the sticking probability data lead to the conclusion that these solid-state processes of CO and N2 are very similar under astrophysically relevant conditions. This conclusion affects the explanations for the observed anti-correlations of gaseous CO and N2H+ in pre-stellar and protostellar cores., Comment: 13 pages, 7 figures, plus appendix of 2 pages containing 2 figures, Accepted by A&A

Absorption and emission lines originating from the nu3 C-H stretching manifold of gas phase CH4 were discovered in the high resolution (R=25,000) infrared L band spectrum along the line of sight toward NGC 7538 : IRS9. These observations provide a diagnostic of the complex dynamics and chemistry in a massive star forming region. The line shapes resemble P Cygni profiles with the absorption and emission components shifted by ~7 km/s with respect to the systemic velocity. Similar velocity components were observed in CO at 4.7 um, but in contrast to CH4, the CO shows deep absorption due to a high velocity outflow as well as absorption at the systemic velocity due to the cold outer envelope. It is concluded that the gas phase CH4 abundance varies by an order of magnitude in this line of sight: it is low in the envelope and the outflow (X[CH4]<0.4e-6), and at least a factor of 10 larger in the central core. The discovery of solid CH4 in independent ground and space based data sets shows that methane is nearly entirely frozen onto grains in the envelope. It thus appears that CH4 is formed by grain surface reactions, evaporates into the gas phase in the warm inner regions of protostellar cores and is efficiently destroyed in shocks related to outflows., Comment: Scheduled for publication in ApJ 615, 01 Nov. 2004. 11 pages

Molecular oxygen and nitrogen are difficult to observe since they are infrared inactive and radio quiet. The low O2 abundances found so far combined with general considerations of dense cloud conditions suggest molecular oxygen is frozen out at low temperatures (< 20 K) in the shielded inner regions of cloud cores. In solid form O2 and N2 can only be observed as adjuncts within other ice constituents, like CO. In this work we focus on fundamental properties of N2 and O2 in CO ice-gas systems, e.g. desorption characteristics and sticking probabilities at low temperatures for different ice morphologies.