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Binary interactions have been proposed to explain a variety of circumstellar structures seen around evolved stars, including asymptotic giant branch (AGB) stars and planetary nebulae. Studies resolving the circumstellar envelopes of AGB stars have revealed spirals, discs and bipolar outflows, with shaping attributed to interactions with a companion. For the first time, we have used a combined chemical and dynamical analysis to reveal a highly eccentric and long-period orbit for W Aquilae, a binary system containing an AGB star and a main sequence companion. Our results are based on anisotropic SiN emission, the first detections of NS and SiC towards an S-type star, and density structures observed in the CO emission. These features are all interpreted as having formed during periastron interactions. Our astrochemistry-based method can yield stringent constraints on the orbital parameters of long-period binaries containing AGB stars, and will be applicable to other systems., Comment: This version of the article has been accepted for publication, after peer review (when applicable) and is subject to Springer Nature's AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: https://doi.org/10.1038/s41550-023-02154-y

The dusty winds of cool evolved stars are a major contributor of the newly synthesised material enriching the Galaxy and future generations of stars. However, the details of the physics and chemistry behind dust formation and wind launching have yet to be pinpointed. Recent spatially resolved observations show the importance of gaining a more comprehensive view of the circumstellar chemistry, but a comparative study of the intricate interplay between chemistry and physics is still difficult because observational details such as frequencies and angular resolutions are rarely comparable. Aiming to overcome these deficiencies, ATOMIUM is an ALMA Large Programme to study the physics and chemistry of the circumstellar envelopes of a diverse set of oxygen-rich evolved stars under homogeneous observing conditions at three angular resolutions between ~0.02"-1.4". Here we summarize the molecular inventory of these sources, and the correlations between stellar parameters and molecular content. Seventeen oxygen-rich or S-type asymptotic giant branch (AGB) and red supergiant (RSG) stars have been observed in several tunings with ALMA Band 6, targeting a range of molecules to probe the circumstellar envelope and especially the chemistry of dust formation close to the star. We systematically assigned the molecular carriers of the spectral lines and measured their spectroscopic parameters and the angular extent of the emission of each line from integrated intensity maps. Across the ATOMIUM sample, we detect 291 transitions of 24 different molecules and their isotopologues. This includes several first detections in oxygen-rich AGB/RSG stars: PO v=1, SO2 v1=1 and v2=2, and several high energy H2O transitions. We also find several first detections in S-type AGB stars: vibrationally excited HCN v2=2,3 and SiS v=4,5,6, as well as first detections of the molecules SiC, AlCl, and AlF in W Aql..., Comment: 19 pages plus appendices, forthcoming publication in Astronomy & Astrophysics

Water and the hydroxyl radical are major constituents of the envelope of O-rich late-type stars. Transitions involving energy levels that are highly excited have been observed in both H$_2$O and OH. These and more recently discovered transitions can now be observed at a high sensitivity and angular resolution with the ALMA Array. Spectra and maps of H$_2$O and OH observed with an angular resolution of 20 to $\sim$200 mas were obtained at two epochs with the ALMA array. Observations with the Compact Array were also used to check for time variability of water transitions. Radiative transfer models of water were revisited to characterize masing conditions and up-to-date chemical models were used for comparison with our observations. Ten rotational transitions of H$_2$O with energies up to 9000 K were observed in various vibrational states. All but one are new detections in space, and from these we have derived accurate rest frequencies. Hyperfine split $\Lambda$-doubling transitions in v = 0, J = 27/2 and 29/2 levels of the $^2\Pi_{3/2}$ state and, $J = 33/2$ and 35/2 of the $^2\Pi_{1/2}$ state of OH with excitation energies up to 8900 K were also observed. Four of these transitions are new detections in space. Combining our measurements with earlier observations of OH, the v = 0 and v = 1 $\Lambda$-doubling frequencies have been improved. Our H$_2$O maps show compact emission and extensions up to twelve stellar radii or more. The 268.149 GHz emission line of water in the v$_2$ = 2 state is time variable, tends to be masing with dominant radiative pumping, and is widely excited. The widespread but weaker 262.898 GHz water line in v$_2$ = 1 also shows signs of maser emission. Emission and absorption of both H$_2$O and OH reveal an infall of matter and complex kinematics influenced by binarity. From our observed column densities, we derived OH/H$_2$O abundance ratios in a few stars., Comment: 41 pages with references and 25 figures in main text. 4 Tables in Appendix A. 10 figures in Appendix B. 2 figures in Appendix C. 14 figures in Appendix D. 5 figures in Appendix E. 2 figures in Appendix F

Aims. Through the ATOMIUM project, based on an ALMA large program, we aim to present a consistent view of a sample of 17 nearby cool evolved stars (Aymptotic Giant Branch and red supergiant stars). Methods. Here we present VLT/SPHERE-ZIMPOL polarimetric maps obtained in the visible of 14 out of the 17 ATOMIUM sources. They were obtained contemporaneously with the ALMA high spatial resolution data. To help interpret the polarized signal, we produced synthetic maps of light scattering by dust, through 3D radiative transfer simulations with the RADMC3D code. Results. The degree of linear polarization (DoLP) observed by ZIMPOL spreads across several optical filters. We infer that it primarily probes dust located just outside of the point spread function, and in or near the plane of the sky, with a total optical depth close to unity in the line of sight, representing only a fraction of the total circumstellar dust. The maximum DoLP ranges from 0.03-0.38 depending on the source, fractions that can be reproduced by our 3D pilot models for grains composed of common dust species. The spatial structure of the DoLP shows a diverse set of shapes. Only for three sources do we note a correlation between the ALMA CO and SiO lines, which trace the gas density, and the DoLP, which traces the dust. Conclusion. The clumpiness of the DoLP and the lack of a consistent correlation between the gas and the dust location show that, in the inner circumstellar environment (CSE), dust formation occurs at very specific sites. This has potential consequences for the derived mass-loss rates and dust-to-gas ratio in the inner region of the CSE. Except for $\pi^1$~Gru and perhaps GY Aql, we do not detect interactions between the circumstellar wind and the hypothesized companions that shape the wind at larger scales. This suggests that the orbits of any other companions are tilted out of the plane of the sky., Comment: Accepted for publication in Astronomy & Astrophysics. 22 pages, 15 figures, 5 tables

This overview paper presents ATOMIUM, a Large Programme in Cycle 6 with the Atacama Large Millimeter-submillimeter Array (ALMA). The goal of ATOMIUM is to understand the dynamics and the gas phase and dust formation chemistry in the winds of evolved asymptotic giant branch (AGB) and red supergiant (RSG) stars. A more general aim is to identify chemical processes applicable to other astrophysical environments. 17 oxygen-rich AGB and RSG stars spanning a range in (circum)stellar parameters and evolutionary phases were observed in a homogeneous observing strategy allowing for an unambiguous comparison. Data were obtained between 213.83 and 269.71 GHz at high (0.025-0.050 arcsec), medium (0.13-0.24 arcsec), and low (about 1 arcsec) angular resolution. The sensitivity per 1.3 km/s channel was 1.5-5 mJy/beam. 13 molecules were designated as primary molecules in the survey: CO, SiO, AlO, AlOH, TiO, TiO2, HCN, SO, SO2, SiS, CS, H2O, and NaCl. The scientific motivation, survey design, sample properties, data reduction, and an overview of the data products are described; and we highlight one scientific result - the wind kinematics of the ATOMIUM sources. The ATOMIUM sources often have a slow wind acceleration, and a fraction of the gas reaches a velocity which can be up to a factor of two times larger than previously reported terminal velocities assuming isotropic expansion, and the wind kinematic profiles establish that the radial velocity described by the momentum equation for a spherical wind structure cannot capture the complexity of the velocity field. In 15 sources, some molecular transitions other than 12CO v=0 J=2-1 reach a higher outflow velocity, with a spatial emission zone that is often greater than 30 stellar radii, but much less than the extent of CO. Binary interaction with a (sub)stellar companion might (partly) explain the non-monotonic behaviour of the projected velocity field.

S-type asymptotic giant branch (AGB) stars are thought to be intermediates in the evolution of oxygen- to carbon-rich AGB stars. The chemical compositions of their circumstellar envelopes are also intermediate, but have not been studied in as much detail as their carbon- and oxygen-rich counterparts. We aim to determine the abundances of AlCl and AlF from rotational lines, which have been observed for the first time towards an S-type AGB star, W Aql. In combination with models based on PACS observations, we aim to update our chemical kinetics network based on these results. We analyse ALMA observations towards W Aql of AlCl in the ground and first two vibrationally excited states and AlF in the ground vibrational state. Using radiative transfer models, we determine the abundances and spatial abundance distributions of Al$^{35}$Cl, Al$^{37}$Cl, and AlF. We also model HCl and HF emission and compare these models to PACS spectra to constrain the abundances of these species. AlCl is found in clumps very close to the star, with emission confined within 0.1$^{\prime\prime}$ of the star. AlF emission is more extended, with faint emission extending 0.2$^{\prime\prime}$ to 0.6$^{\prime\prime}$ from the continuum peak. We find peak abundances, relative to H$_2$, of $1.7\times 10^{-7}$ for Al$^{35}$Cl, $7\times 10^{-8}$ for Al$^{37}$Cl and $1\times 10^{-7}$ for AlF. From the PACS spectra, we find abundances of $9.7\times 10^{-8}$ and $\leq 10^{-8}$, relative to H$_2$, for HCl and HF, respectively. The AlF abundance exceeds the solar F abundance, indicating that fluorine synthesised in the AGB star has already been dredged up to the surface of the star and ejected into the circumstellar envelope. From our analysis of chemical reactions in the wind, we conclude that AlF may participate in the dust formation process, but we cannot fully explain the rapid depletion of AlCl seen in the wind., Comment: Accepted for publication in Astronomy & Astrophysics

Evolved low- to intermediate-mass stars are known to shed their gaseous envelope into a large, dusty, molecule-rich circumstellar nebula which typically develops a high degree of structural complexity. Most of the large-scale, spatially correlated structures in the nebula are thought to originate from the interaction of the stellar wind with a companion. As part of the Atomium large programme, we observed the M-type asymptotic giant branch (AGB) star R Hydrae with ALMA. The morphology of the inner wind of R Hya, which has a known companion at ~3500 au, was determined from maps of CO and SiO obtained at high angular resolution. A map of the CO emission reveals a multi-layered structure consisting of a large elliptical feature at an angular scale of ~10'' that is oriented along the north-south axis. The wind morphology within the elliptical feature is dominated by two hollow bubbles. The bubbles are on opposite sides of the AGB star and lie along an axis with a position angle of ~115 deg. Both bubbles are offset from the central star, and their appearance in the SiO channel maps indicates that they might be shock waves travelling through the AGB wind. An estimate of the dynamical age of the bubbles yields an age of the order of 100 yr, which is in agreement with the previously proposed elapsed time since the star last underwent a thermal pulse. When the CO and SiO emission is examined on subarcsecond angular scales, there is evidence for an inclined, differentially rotating equatorial density enhancement, strongly suggesting the presence of a second nearby companion. The position angle of the major axis of this disc is ~70 deg in the plane of the sky. We tentatively estimate that a lower limit on the mass of the nearby companion is ~0.65 Msol on the basis of the highest measured speeds in the disc and the location of its inner rim at ~6 au from the AGB star., Comment: 21 pages, 23 figures

Rotational transitions in vibrationally excited AlO and TiO -- two possible precursors of dust -- were observed in the 300 GHz range (1 mm wavelength) towards the oxygen rich AGB stars R Dor and IK Tau with ALMA, and vibrationally excited AlO was observed towards the red supergiant VY CMa with the SMA. The $J=11 \to 10$ transition of TiO in the $v=1~{\rm{and}}~2$ levels, and the $N = 9 \to 8$ transition in the $v=2$ level of AlO were identified towards R Dor; the $J=11 \to 10$ line of TiO was identified in the $v=1$ level towards IK Tau; and two transitions in the $v=1~{\rm{and}}~2$ levels of AlO were identified towards VY CMa. The newly-derived high vibrational temperature of TiO and AlO in R Dor of $1800 \pm 200$ K, and prior measurements of the angular extent confirm that the majority of the emission is from a region within $\lesssim2R_{\star}$ of the central star. A full radiative transfer analysis of AlO in R Dor yielded a fractional abundance of $\sim$3% of the solar abundance of Al. From a similar analysis of TiO a fractional abundance of $\sim78$% of the solar abundance of Ti was found. The observations provide indirect evidence that TiO is present in a rotating disk close to the star. Further observations in the ground and excited vibrational levels are needed to determine whether AlO, TiO, and TiO$_2$ are seeds of the Al$_2$O$_3$ dust in R Dor, and perhaps in the gravitationally bound dust shells in other AGB stars with low mass loss rates., Comment: Accepted for publication in ApJ

Binary interactions dominate the evolution of massive stars, but their role is less clear for low- and intermediate-mass stars. The evolution of a spherical wind from an asymptotic giant branch (AGB) star into a nonspherical planetary nebula (PN) could be due to binary interactions. We observed a sample of AGB stars with the Atacama Large Millimeter/submillimeter Array (ALMA) and found that their winds exhibit distinct nonspherical geometries with morphological similarities to planetary nebulae (PNe). We infer that the same physics shapes both AGB winds and PNe; additionally, the morphology and AGB mass-loss rate are correlated. These characteristics can be explained by binary interaction. We propose an evolutionary scenario for AGB morphologies that is consistent with observed phenomena in AGB stars and PNe., Comment: 19 pages main journal, 97 pages Supplementary Information

We present and analyse SO and SO$_2$, recently observed with high angular resolution and sensitivity in a spectral line survey with ALMA, for two oxygen-rich AGB stars: the low mass-loss rate R Dor and high mass-loss rate IK Tau. We analyse 8 lines of SO detected towards both stars, 78 lines of SO$_2$detected towards R Dor and 52 lines of SO$_2$ detected towards IK Tau. We detect several lines of $^{34}$SO, $^{33}$SO and $^{34}$SO$_2$ towards both stars, and tentatively S$^{18}$O towards R Dor, and hence derive isotopic ratios for these species. The spatially resolved observations show us that the two sulphur oxides are co-located towards R Dor and trace out the same wind structures in the circumstellar envelope (CSE). Much of the emission is well reproduced with a Gaussian abundance distribution spatially centred on the star. Emission from the higher energy levels of SO and SO$_2$ towards R Dor provide evidence in support of a rotating inner region of gas identified in earlier work. The new observations allow us to refine the abundance distribution of SO in IK Tau derived from prior observations with single antennas, and confirm the distribution is shell-like with the peak in the fractional abundance not centred on the star. The confirmation of different types of SO abundance distributions will help fine-tune chemical models and allows for an additional method to discriminate between low and high mass-loss rates for oxygen-rich AGB stars., Comment: Accepted for publication in MNRAS

Using ALMA, we observed the stellar wind of two oxygen-rich Asymptotic Giant Branch (AGB) stars, IK Tau and R Dor, between 335 and 362 GHz. One aim was to detect metal oxides and metal hydroxides (AlO, AlOH, FeO, MgO, MgOH), some of which are thought to be direct precursors of dust nucleation and growth. We report on the potential first detection of FeO (v=0, Omega=4, J=11-10) in RDor (mass-loss rate, Mdot, ~1e-7 Msun/yr). The presence of FeO in IK Tau (Mdot~5e-6 Msun/yr) cannot be confirmed due to a blend with 29SiS, a molecule that is absent in R Dor. The detection of AlO in R Dor and of AlOH in IK Tau was reported earlier by Decin et al. (2017). All other metal oxides and hydroxides, as well as MgS, remain undetected. We derive a column density N(FeO) of 1.1+/-0.9e15 cm^{-2} in R Dor, or a fractional abundance [FeO/H]~1.5e-8 accounting for non-LTE effects. The derived fractional abundance [FeO/H] is a factor ~20 larger than conventional gas-phase chemical kinetic predictions. This discrepancy may be partly accounted for by the role of vibrationally excited OH in oxidizing Fe, or may be evidence for other currently unrecognised chemical pathways producing FeO. Assuming a constant fractional abundance w.r.t. H_2, the upper limits for the other metals are [MgO/H_2] <5.5e-10 (R Dor) and <7e-11 (IK Tau), [MgOH/H_2] <9e-9 (R Dor) and <1e-9 (IK Tau), [CaO/H_2] <2.5e-9 (R Dor) and <1e-10 (IK Tau), [CaOH/H_2] <6.5e-9 (R Dor) and <9e-10 (IK Tau), and [MgS/H_$] <4.5e-10 (R Dor) and <6e-11 (IK Tau). The retrieved upper limit abundances for these latter molecules are in accord with the chemical model predictions., Comment: 14 pages (including appendices), accepted for publication by Astrophysical Journal

Linear carbon chains are common in various types of astronomical molecular sources. Possible formation mechanisms involve both bottom-up and top-down routes. We have carried out a combined observational and modeling study of the formation of carbon chains in the C-star envelope IRC+10216, where the polymerization of acetylene and hydrogen cyanide induced by ultraviolet photons can drive the formation of linear carbon chains of increasing length. We have used ALMA to map the emission of 3 mm rotational lines of the hydrocarbon radicals C2H, C4H, and C6H, and the CN-containing species CN, C3N, HC3N, and HC5N with an angular resolution of 1". The spatial distribution of all these species is a hollow, 5-10" wide, spherical shell located at a radius of 10-20" from the star, with no appreciable emission close to the star. Our observations resolve the broad shell of carbon chains into thinner sub-shells which are 1-2" wide and not fully concentric, indicating that the mass loss process has been discontinuous and not fully isotropic. The radial distributions of the species mapped reveal subtle differences: while the hydrocarbon radicals have very similar radial distributions, the CN-containing species show more diverse distributions, with HC3N appearing earlier in the expansion and the radical CN extending later than the rest of the species. The observed morphology can be rationalized by a chemical model in which the growth of polyynes is mainly produced by rapid gas-phase chemical reactions of C2H and C4H radicals with unsaturated hydrocarbons, while cyanopolyynes are mainly formed from polyynes in gas-phase reactions with CN and C3N radicals., Comment: Accepted for publication in A&A

The formation of silicate dust in oxygen-rich envelopes of evolved stars is thought to be initiated by formation of seed particles that can withstand the high temperatures close to the stellar photosphere and act as condensation cores farther away from the star. Candidate species considered as first condensates are TiO and TiO$_2$. We aim to identify and characterize the circumstellar gas-phase chemistry of titanium that leads to the formation of solid titanium compounds in the envelope of $o$ Cet, the prototypical Mira, and seek an observational verification of whether titanium oxides play a major role in the onset of dust formation in M-type AGB stars. We present high angular-resolution ALMA observations at submillimeter (submm) wavelengths supplemented by APEX and Herschel spectra of the rotational features of TiO and TiO$_2$. In addition, circumstellar features of TiO and TiI are identified in optical spectra which cover multiple pulsation cycles of $o$ Cet. The submm ALMA data reveal TiO and TiO$_2$ bearing gas within the extended atmosphere of Mira. While TiO is traceable up to a radius (FWHM/2) of 4.0 R$_{\star}$, TiO$_2$ extends as far as 5.5 R$_{\star}$ and unlike TiO appears to be anisotropically distributed. Optical spectra display variable emission of TiI and TiO from inner parts of the extended atmosphere (<3 R$_{\star}$). Chemical models which include shocks are in general agreement with the observations of gas-phase titanium-bearing molecules. It is unlikely that substantial amounts of titanium is locked up in solids because the abundance of the gaseous titanium species is very high. In particular, formation of hot titanium-rich condensates is very improbable because we find no traces of their hot precursor species in the gas phase. It therefore appears unlikely that the formation of dust in Mira, and possibly other M-type AGB stars, is initiated by titanium oxides., Comment: 19 pages plus spectral atlas of the TiO gamma' band in 1998-2014 submitted to A&A

Context: Dust is efficiently produced by cool giant stars, but the condensation of inorganic dust is poorly understood. Aims: Identify and characterize aluminum bearing species in the circumstellar gas of Mira ($o$ Ceti) in order to elucidate their role in the production of Al$_2$O$_3$ dust. Methods: Multiepoch spectral line observations at (sub-)millimeter, far-infrared, and optical wavelengths including: maps with ALMA which probe the gas distribution in the immediate vicinity of the star at ~30 mas; observations with ALMA, APEX, and Herschel in 2013-2015 for studying cycle and inter-cycle variability of the rotational lines of Al bearing molecules; optical records as far back as 1965 to examine variations in electronic transitions over time spans of days to decades; and velocity measurements and excitation analysis of the spectral features which constrain the physical parameters of the gas. Results: Three diatomic molecules AlO, AlOH, and AlH, and atomic Al I are the main observable aluminum species in Mira, although a significant fraction of aluminum might reside in other species that have not yet been identified. Strong irregular variability in the (sub-)millimeter and optical features of AlO (possibly the direct precursor of Al$_2$O$_3$) indicates substantial changes in the excitation conditions, or varying abundance that is likely related to shocks in the star. The inhomogeneous distribution of AlO might influence the spatial and temporal characteristics of dust production. Conclusions: We are unable to quantitatively trace aluminum depletion from the gas, but the rich observational material constrains time dependent chemical networks. Future improvements should include spectroscopic characterization of higher aluminum oxides, coordinated observations of dust and gas species at different variability phases, and tools to derive abundances in shock excited gas., Comment: submitted to A&A, 23 pages plus an atlas of spectral variability of Mira in Al-bearing species since 1965 (90 pages total)

The partially deuterated linear isomer HDCCC of the ubiquitous cyclic carbene ($c$-C$_3$H$_2$) was observed in the starless cores TMC-1C and L1544 at 96.9 GHz, and a confirming line was observed in TMC-1 at 19.38 GHz. To aid the identification in these narrow line sources, four centimetre-wave rotational transitions (two in the previously reported $K_a =0$ ladder, and two new ones in the $K_a =1$ ladder), and 23 transitions in the millimetre band between 96 and 272 GHz were measured in high-resolution laboratory spectra. Nine spectroscopic constants in a standard asymmetric top Hamiltonian allow the principal transitions of astronomical interest in the $K_a \le 3$ rotational ladders to be calculated to within 0.1 km s$^{-1}$ in radial velocity up to 400 GHz. Conclusive evidence for the identification of the two astronomical lines of HDCCC was provided by the $V_{\rm{LSR}}$ which is the same as that of the normal isotopic species (H$_2$CCC) in the three narrow line sources. In these sources, deuterium fractionation in singly substituted H$_2$CCC (HDCCC/H$_2$CCC $\sim4\%\text{-}19\%$) is comparable to that in $c$-C$_3$H$_2$ ($c$-C$_3$H$_2$/$c$-C$_3$HD $\sim5\%\text{-}17\%$), and similarly in doubly deuterated $c$-C$_3$H$_2$ ($c$-C$_3$D$_2$/$c$-C$_3$HD $\sim3\%\text{-}17\%$), implying that the efficiency of the deuteration processes in the H$_2$CCC and $c$-C$_3$H$_2$ isomers are comparable in dark clouds., Comment: Accepted for publication in A&A

We report the discovery in space of a disilicon species, SiCSi, from observations between 80 and 350 GHz with the IRAM 30m radio telescope. Owing to the close coordination between laboratory experiments and astrophysics, 112 lines have now been detected in the carbon-rich star CWLeo. The derived frequencies yield improved rotational and centrifugal distortion constants up to sixth order. From the line profiles and interferometric maps with the Submillimeter Array, the bulk of the SiCSi emis- sion arises from a region of 6 arcseconds in radius. The derived abundance is comparable to that of SiC2. As expected from chemical equilibrium calculations, SiCSi and SiC2 are the most abundant species harboring a SiC bond in the dust formation zone and certainly both play a key role in the formation of SiC dust grains., Comment: To be published in the Astrophysical Journal Letters; Accepted May 6 2015

Rotational spectra in four new excited vibrational levels of the linear carbon chain radical C$_4$H radical were observed in the millimeter band between 69 and 364 GHz in a low pressure glow discharge, and two of these were observed in a supersonic molecular beam between 19 and 38 GHz. All have rotational constants within 0.4% of the $^2\Sigma^+$ ground vibrational state of C$_4$H and were assigned to new bending vibrational levels, two each with $^2\Sigma$ and $^2\Pi$ vibrational symmetry. The new levels are tentatively assigned to the $1\nu_6$ and $1\nu_5$ bending vibrational modes (both with $^2\Pi$ symmetry), and the $1\nu_6 + 1\nu_7$ and $1\nu_5 + 1\nu_6$ combination levels ($^2\Sigma$ symmetry) on the basis of the derived spectroscopic constants, relative intensities in our discharge source, and published laser spectroscopic and quantum calculations. Prior spectroscopic constants in the $1\nu_7$ and $2\nu_7$ levels were refined. Also presented are interferometric maps of the ground state and the $1\nu_7$ level obtained with the SMA near 257 GHz which show that C$_4$H is present near the central star in IRC+10216. We found no evidence with the SMA for the new vibrationally excited levels of C$_4$H at a peak flux density averaged over a $3^{\prime\prime}$ synthesized beam of $\ge 0.15$ Jy/beam in the 294-296 and 304-306 GHz range, but it is anticipated that rotational lines in the new levels might be observed in IRC+10216 when ALMA attains its full design capability., Comment: The Astrophysical Journal Supplement Series, in press. 25 pages with 7 figures

A spectral line survey of the oxygen-rich red supergiant VY Canis Majoris was made between 279 and 355 GHz with the Submillimeter Array. Two hundred twenty three spectral features from 19 molecules (not counting isotopic species of some of them) were observed, including the rotational spectra of TiO, TiO2, and AlCl for the first time in this source. The parameters and an atlas of all spectral features is presented. Observations of each line with a synthesized beam of ~0.9 arcsec, reveal the complex kinematics and morphology of the nebula surrounding VY CMa. Many of the molecules are observed in high lying rotational levels or in excited vibrational levels. From these, it was established that the main source of the submillimeter-wave continuum (dust) and the high excitation molecular gas (the star) are separated by about 0.15 arcsec. Apparent coincidences between the molecular gas observed with the SMA, and some of the arcs and knots observed at infrared wavelengths and in the optical scattered light by the Hubble Space Telescope are identified. The observations presented here provide important constraints on the molecular chemistry in oxygen-dominated circumstellar environments and a deeper picture of the complex circumstellar environment of VY CMa., Comment: extended version of a paper accepted to ApJS. 67 pages, includes a spectral atlas

Phosphorus-bearing compounds have only been studied in the circumstellar environments (CSEs) of the asymptotic giant branch (AGB) star IRC +10216 and the protoplanetary nebula CRL 2688, both C-rich objects, and the O-rich red supergiant VY CMa. The current chemical models cannot reproduce the high abundances of PO and PN derived from observations of VY CMa. No observations have been reported of phosphorus in the CSEs of O-rich AGB stars. We aim to set observational constraints on the phosphorous chemistry in the CSEs of O-rich AGB stars, by focussing on the Mira-type variable star IK Tau. Using the IRAM 30m telescope and the Submillimeter Array (SMA), we observed four rotational transitions of PN (J=2-1,3-2,6-5,7-6) and four of PO (J=5/2-3/2,7/2-5/2,13/2-11/2,15/2-13/2). The IRAM 30m observations were dedicated line observations, while the SMA data come from an unbiased spectral survey in the frequency range 279-355 GHz. We present the first detections of PN and PO in an O-rich AGB star and estimate abundances X(PN/H2) of about 3x10^-7 and X(PO/H2) in the range 0.5-6.0x10^-7. This is several orders of magnitude higher than what is found for the C-rich AGB star IRC +10216. The diameter (<=0.7") of the PN and PO emission distributions measured in the interferometric data corresponds to a maximum radial extent of about 40 stellar radii. The abundances and the spatial occurrence of the molecules are in very good agreement with the results reported for VY CMa. We did not detect PS or PH3 in the survey. We suggest that PN and PO are the main carriers of phosphorus in the gas phase, with abundances possibly up to several 10^-7. The current chemical models cannot account for this, underlining the strong need for updated chemical models that include phosphorous compounds., Comment: Accepted for publication in Astronomy & Astrophysics, 10 pages, 8 figures

The formation of inorganic dust in circumstellar environments of evolved stars is poorly understood. Spectra of molecules thought to be most important for the nucleation, i.e. AlO, TiO, and TiO2, have been recently detected in the red supergiant VY CMa. These molecules are effectively formed in VY CMa and the observations suggest that non-equilibrium chemistry must be involved in their formation and nucleation into dust. In addition to exploring the recent observations of VY CMa, we briefly discuss the possibility of detecting these molecules in the dust-poor circumstellar environment of Betelgeuse., Comment: contribution to Betelgeuse Workshop 2012: "The physics of Red Supergiants: recent advances and open questions", 26-29 Nov 2012 Paris (France)

We report the first detection of pure rotational transitions of TiO and TiO_2 at (sub-)millimeter wavelengths towards the red supergiant VY CMa. A rotational temperature, T_rot, of about 250 K was derived for TiO_2. Although T_rot was not well constrained for TiO, it is likely somewhat higher than that of TiO_2. The detection of the Ti oxides confirms that they are formed in the circumstellar envelopes of cool oxygen-rich stars and may be the "seeds" of inorganic-dust formation, but alternative explanations for our observation of TiO and TiO_2 in the cooler regions of the envelope cannot be ruled out at this time. The observations suggest that a significant fraction of the oxides is not converted to dust, but instead remains in the gas phase throughout the outflow., Comment: to appear in Astronomy and Astrophysics

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., Comment: 5 pages, 4 figures; accepted for publication in A&A Letters

Pure rotational spectra of three polycyclic aromatic hydrocarbons - acenaphthene, acenaphthylene and fluorene - have been obtained by Fourier transform microwave spectroscopy of a molecular beam and subsequently by millimeter wave absorption spectroscopy for acenaphthene and fluorene. The data presented here will be useful for deep radio astronomical searches for PAHs employing large radio telecopes., Comment: 2 pages, 1 figure (uses iaus.sty), to appear in IAU Symposium No. 231, Astrochemistry - Recent Successes and Current Challenges, eds. D. C. Lis, G. A. Blake & E. Herbst (Cambridge Univ. Press)

Two consecutive rotational transitions of the long cyanopolyyne HC11N, J=39-38, and J=38-37, have been detected in the cold dust cloud TMC-1 at the frequencies expected from recent laboratory measurements by Travers et al. (1996), and at about the expected intensities. The astronomical lines have a mean radial velocity of 5.8(1) km/s, in good agreement with the shorter cyanopolyynes HC7N and HC9N observed in this very sharp-lined source [5.82(5) and 5.83(5) km/s, respectively]. The column density of HC11N is calculated to be 2.8x10^(11) cm^(-2). The abundance of the cyanopolyynes decreases smoothly with length to HC11N, the decrement from one to the next being about 6 for the longer carbon chains., Comment: plain tex 10 pages plus 3 ps fig files

The cumulene carbenes are important components of hydrocarbon chemistry in low mass star forming cores. Here we report the first astronomical detection of the long chain cumulene carbene H_2C_6 in the interstellar cloud TMC1, from observations of two of its rotational transitions: $J_{K,K'} = 7_{1,7} \rightarrow 6_{1,6}$ at 18.8 GHz and $8_{1,8} \rightarrow 7_{1,7}$ at 21.5 GHz, using NASA's Deep Space Network 70 m antenna at Goldstone, California. In addition we also observed the shorter cumulene carbene, H_2C_4 at the same position. The fractional abundance of H_2C_6 relative to H_2 is about $4.7 \times 10^{-11}$ and H_2C_4 is about $1.1 \times 10^{-9}$. The abundance of H_2C_6 is in fairly good agreement with gas phase chemical models for young molecular cloud cores, but the abundance of H_2C_4 is significantly larger than predicted., Comment: plain tex