Formation of the methyl cation by photochemistry in a protoplanetary disk.

Forty years ago, it was proposed that gas-phase organic chemistry in the interstellar medium can be initiated by the methyl cation CH3+ (refs. 1-3), but so far it has not been observed outside the Solar System4,5. Alternative routes involving processes on grain surfaces have been invoked6,7. Here we report James Webb Space Telescope observations of CH3+ in a protoplanetary disk in the Orion star-forming region. We find that gas-phase organic chemistry is activated by ultraviolet irradiation.

Compression and ablation of the photo-irradiated molecular cloud the Orion Bar.

The Orion Bar is the archetypal edge-on molecular cloud surface illuminated by strong ultraviolet radiation from nearby massive stars. Our relative closeness to the Orion nebula (about 1,350 light years away from Earth) means that we can study the effects of stellar feedback on the parental cloud in detail. Visible-light observations of the Orion Bar show that the transition between the hot ionized gas and the warm neutral atomic gas (the ionization front) is spatially well separated from the transition between atomic and molecular gas (the dissociation front), by about 15 arcseconds or 6,200 astronomical units (one astronomical unit is the Earth-Sun distance). Static equilibrium models used to interpret previous far-infrared and radio observations of the neutral gas in the Orion Bar (typically at 10-20 arcsecond resolution) predict an inhomogeneous cloud structure comprised of dense clumps embedded in a lower-density extended gas component. Here we report one-arcsecond-resolution millimetre-wave images that allow us to resolve the molecular cloud surface. In contrast to stationary model predictions, there is no appreciable offset between the peak of the H2 vibrational emission (delineating the H/H2 transition) and the edge of the observed CO and HCO+ emission. This implies that the H/H2 and C+/C/CO transition zones are very close. We find a fragmented ridge of high-density substructures, photoablative gas flows and instabilities at the molecular cloud surface. The results suggest that the cloud edge has been compressed by a high-pressure wave that is moving into the molecular cloud, demonstrating that dynamical and non-equilibrium effects are important for the cloud evolution.

Bringing high spatial resolution to the far-infrared: A giant leap for astrophysics.

The far-infrared (FIR) regime is one of the wavelength ranges where no astronomical data with sub-arcsecond spatial resolution exist. None of the medium-term satellite projects like SPICA, Millimetron, or the Origins Space Telescope will resolve this malady. For many research areas, however, information at high spatial and spectral resolution in the FIR, taken from atomic fine-structure lines, from highly excited carbon monoxide (CO), light hydrides, and especially from water lines would open the door for transformative science. A main theme will be to trace the role of water in proto-planetary discs, to observationally advance our understanding of the planet formation process and, intimately related to that, the pathways to habitable planets and the emergence of life. Furthermore, key observations will zoom into the physics and chemistry of the star-formation process in our own Galaxy, as well as in external galaxies. The FIR provides unique tools to investigate in particular the energetics of heating, cooling, and shocks. The velocity-resolved data in these tracers will reveal the detailed dynamics engrained in these processes in a spatially resolved fashion, and will deliver the perfect synergy with ground-based molecular line data for the colder dense gas.

Experimental studies of H13CO+ recombining with electrons at energies between 2-50,000 meV.

An investigation into the dissociative recombination process for H(13)CO(+) using merged ion-electron beam methods has been performed at the heavy ion storage ring CRYRING, Stockholm, Sweden. We have measured the branching fractions of the different product channels at ∼ 0 eV collision energy to be the following: CO + H 87 ± 2%, OH + C 9 ± 2%, and O + CH 4 ± 2%. The formation of electronically excited CO in the dominant reaction channel has also been studied, and we report the following tentative branching fractions for the different CO product electronic states: CO(X (1)Σ(+)) + H, 54 ± 10%; CO(a (3)Π) + H, 23 ± 4%; and CO(a' (3)Σ(+)) + H, 23 ± 4%. The absolute cross section between ∼ 2-50 000 meV was measured and showed resonance structures between 3 and 15 eV. The cross section was fitted in the energy range relevant to astrophysics, i.e., between 1 and 300 meV, and was found to follow the expression σ = 1.3 ± 0.3 × 10(-16) E(-1.29 ± 0.05) cm(2) and the corresponding thermal rate constant was determined to be k(T) = 2.0 ± 0.4 × 10(-7)(T/300)(-0.79 ± 0.05) cm(3) s(-1). Radioastronomical observations with the IRAM 30 m telescope of HCO(+) toward the Red Rectangle yielded an upper column density limit of 4 × 10(11) cm(-2) of HCO(+) at the 1σ level in that object, indicating that previous claims that the dissociative recombination of HCO(+) plays an important role in the production of excited CO molecules emitting the observed Cameron bands in that object are not supported.

CH2D(+), the search for the holy grail.

CH2D+, the singly deuterated counterpart of CH3(+), offers an alternative way to mediate formation of deuterated species at temperatures of several tens of Kelvin, as compared to the release of deuterated species from grains. We report a longstanding observational search for this molecular ion, whose rotational spectroscopy is not yet completely secure. We summarize the main spectroscopic properties of this molecule and discuss the chemical network leading to the formation of CH2D+, with explicit account of the ortho/para forms of H2, H3(+), and CH3(+). Astrochemical models support the presence of this molecular ion in moderately warm environments at a marginal level.

Determination of the ortho to para ratio of H2Cl+ and H2O+ from submillimeter observations.

The opening of the submillimeter sky with the Herschel Space Observatory has led to the detection of new interstellar molecular ions, H2O(+), H2Cl(+), and HCl(+), which are important intermediates in the synthesis of water vapor and hydrogen chloride. In this paper, we report new observations of H2O(+) and H2Cl(+) performed with both Herschel and ground-based telescopes, to determine the abundances of their ortho and para forms separately and derive the ortho-to-para ratio. At the achieved signal-to-noise ratio, the observations are consistent with an ortho-to-para ratios of 3 for both H2O(+) and H2Cl(+), in all velocity components detected along the lines-of-sight to the massive star-forming regions W31C and W49N. We discuss the mechanisms that contribute to establishing the observed ortho-to-para ratio and point to the need for a better understanding of chemical reactions, which are important for establishing the H2O(+) and H2Cl(+) ortho-to-para ratios.

Oxygen fractionation in dense molecular clouds.

We have developed the first gas-grain chemical model for oxygen fractionation (also including sulphur fractionation) in dense molecular clouds, demonstrating that gas-phase chemistry generates variable oxygen fractionation levels, with a particularly strong effect for NO, SO, O2, and SO2. This large effect is due to the efficiency of the neutral 18O + NO, 18O + SO, and 18O + O2 exchange reactions. The modeling results were compared to new and existing observed isotopic ratios in a selection of cold cores. The good agreement between model and observations requires that the gas-phase abundance of neutral oxygen atoms is large in the observed regions. The S16O/S18O ratio is predicted to vary substantially over time showing that it can be used as a sensitive chemical proxy for matter evolution in dense molecular clouds.

High-speed molecular cloudlets around the Galactic center's supermassive black hole.

We present 1″-resolution ALMA observations of the circumnuclear disk (CND) and the interstellar environment around Sgr A*. The images unveil the presence of small spatial scale 12CO (J=3-2) molecular "cloudlets" (≲20,000 AU size) within the central parsec of the Milky Way, in other words, inside the cavity of the CND, and moving at high speeds, up to 300 km s-1 along the line-of-sight. The 12CO-emitting structures show intricate morphologies: extended and filamentary at high negative-velocities (vLSR ≲-150 km s-1), more localized and clumpy at extreme positive-velocities (vLSR ≳+200 km s-1). Based on the pencil-beam 12CO absorption spectrum toward Sgr A* synchrotron emission, we also present evidence for a diffuse molecular gas component producing absorption features at more extreme negative-velocities (vLSR <-200 km s-1). The CND shows a clumpy spatial distribution traced by the optically thin H13CN (J=4-3) emission. Its motion requires a bundle of non-uniformly rotating streams of slightly different inclinations. The inferred gas density peaks, molecular cores of a few 105 cm-3, are lower than the local Roche limit. This supports that CND cores are transient. We apply the two standard orbit models, spirals vs. ellipses, invoked to explain the kinematics of the ionized gas streamers around Sgr A*. The location and velocities of the 12CO cloudlets inside the cavity are inconsistent with the spiral model, and only two of them are consistent with the Keplerian ellipse model. Most cloudlets, however, show similar velocities that are incompatible with the motions of the ionized streamers or with gas bounded to the central gravity. We speculate that they are leftovers of more massive molecular clouds that fall into the cavity and are tidally disrupted, or that they originate from instabilities in the inner rim of the CND that lead to fragmentation and infall from there. In either case, we show that molecular cloudlets, all together with a mass of several 10 M ⊙, exist around Sgr A*. Most of them must be short-lived, ≲104 yr: photoevaporated by the intense stellar radiation field, G 0≃105.3 to 104.3, blown away by winds from massive stars in the central cluster, or disrupted by strong gravitational shears.

Clustering the Orion B giant molecular cloud based on its molecular emission.

CONTEXT: Previous attempts at segmenting molecular line maps of molecular clouds have focused on using position-position-velocity data cubes of a single molecular line to separate the spatial components of the cloud. In contrast, wide field spectral imaging over a large spectral bandwidth in the (sub)mm domain now allows one to combine multiple molecular tracers to understand the different physical and chemical phases that constitute giant molecular clouds (GMCs). AIMS: We aim at using multiple tracers (sensitive to different physical processes and conditions) to segment a molecular cloud into physically/chemically similar regions (rather than spatially connected components), thus disentangling the different physical/chemical phases present in the cloud. METHODS: We use a machine learning clustering method, namely the Meanshift algorithm, to cluster pixels with similar molecular emission, ignoring spatial information. Clusters are defined around each maximum of the multidimensional Probability Density Function (PDF) of the line integrated intensities. Simple radiative transfer models were used to interpret the astrophysical information uncovered by the clustering analysis. RESULTS: A clustering analysis based only on the J = 1 - 0 lines of three isotopologues of CO proves suffcient to reveal distinct density/column density regimes (nH ~ 100 cm-3, ~ 500 cm-3, and > 1000 cm-3), closely related to the usual definitions of diffuse, translucent and high-column-density regions. Adding two UV-sensitive tracers, the J = 1 - 0 line of HCO+ and the N = 1 - 0 line of CN, allows us to distinguish two clearly distinct chemical regimes, characteristic of UV-illuminated and UV-shielded gas. The UV-illuminated regime shows overbright HCO+ and CN emission, which we relate to a photochemical enrichment effect. We also find a tail of high CN/HCO+ intensity ratio in UV-illuminated regions. Finer distinctions in density classes (nH ~ 7 × 103 cm-3 ~ 4 × 104 cm-3) for the densest regions are also identified, likely related to the higher critical density of the CN and HCO+ (1 - 0) lines. These distinctions are only possible because the high-density regions are spatially resolved. CONCLUSIONS: Molecules are versatile tracers of GMCs because their line intensities bear the signature of the physics and chemistry at play in the gas. The association of simultaneous multi-line, wide-field mapping and powerful machine learning methods such as the Meanshift clustering algorithm reveals how to decode the complex information available in these molecular tracers.

The interstellar chemistry of C3H and C3H2 isomers.

We report the detection of linear and cyclic isomers of C3H and C3H2 towards various starless cores and review the corresponding chemical pathways involving neutral (C3Hx with x=1,2) and ionic (C3Hx+ with x = 1,2,3) isomers. We highlight the role of the branching ratio of electronic Dissociative Recombination (DR) reactions of C3H2+ and C3H3+ isomers showing that the statistical treatment of the relaxation of C3H* and C3H2* produced in these DR reactions may explain the relative c,l-C3H and c,l-C3H2 abundances. We have also introduced in the model the third isomer of C3H2 (HCCCH). The observed cyclic-to-linear C3H2 ratio vary from 110 ± 30 for molecular clouds with a total density around 1×104 molecules.cm-3 to 30 ± 10 for molecular clouds with a total density around 4×105 molecules.cm-3, a trend well reproduced with our updated model. The higher ratio for low molecular cloud densities is mainly determined by the importance of the H + l-C3H2 → H + c-C3H2 and H + t-C3H2 → H + c-C3H2 isomerization reactions.

Spatially resolved images of reactive ions in the Orion Bar,☠☠.

We report high angular resolution (4.9″×3.0″) images of reactive ions SH+, HOC+, and SO+ toward the Orion Bar photodissociation region (PDR). We used ALMA-ACA to map several rotational lines at 0.8 mm, complemented with multi-line observations obtained with the IRAM 30 m telescope. The SH+ and HOC+ emission is restricted to a narrow layer of 2″- to 10″-width (≈800 to 4000 AU depending on the assumed PDR geometry) that follows the vibrationally excited [Formula: see text] emission. Both ions efficiently form very close to the H/H2 transition zone, at a depth of Av≲1 mag into the neutral cloud, where abundant C+, S+, and [Formula: see text] coexist. SO+ peaks slightly deeper into the cloud. The observed ions have low rotational temperatures (Trot≈10-30 K≪Tk) and narrow line-widths (~2-3 km s-1), a factor of ≃2 narrower that those of the lighter reactive ion CH+. This is consistent with the higher reactivity and faster radiative pumping rates of CH+ compared to the heavier ions, which are driven relatively faster toward smaller velocity dispersion by elastic collisions and toward lower Trot by inelastic collisions. We estimate column densities and average physical conditions from an excitation model (n(H2)≈105-106 cm-3, n(e-)≈10 cm-3, and Tk≈200 K). Regardless of the excitation details, SH+ and HOC+ clearly trace the most exposed layers of the UV-irradiated molecular cloud surface, whereas SO+ arises from slightly more shielded layers.

First Detection of Interstellar S2H.

We present the first detection of gas phase S2H in the Horsehead, a moderately UV-irradiated nebula. This confirms the presence of doubly sulfuretted species in the interstellar medium and opens a new challenge for sulfur chemistry. The observed S2H abundance is ~5×10-11, only a factor 4-6 lower than that of the widespread H2S molecule. H2S and S2H are efficiently formed on the UV-irradiated icy grain mantles. We performed ice irradiation experiments to determine the H2S and S2H photodesorption yields. The obtained values are ~1.2×10-3 and <1×10-5 molecules per incident photon for H2S and S2H, respectively. Our upper limit to the S2H photodesorption yield suggests that photo-desorption is not a competitive mechanism to release the S2H molecules to the gas phase. Other desorption mechanisms such as chemical desorption, cosmic-ray desorption and grain shattering can increase the gaseous S2H abundance to some extent. Alternatively, S2H can be formed via gas phase reactions involving gaseous H2S and the abundant ions S+ and SH+. The detection of S2H in this nebula could be therefore the result of the coexistence of an active grain surface chemistry and gaseous photo-chemistry.

The interstellar chemistry of H2C3O isomers.

We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects.

Chemical complexity in the horsehead photodissociation region.

The interstellar medium is known to be chemically complex. Organic molecules with up to 11 atoms have been detected in the interstellar medium, and are believed to be formed on the ices around dust grains. The ices can be released into the gas-phase either through thermal desorption, when a newly formed star heats the medium around it and completely evaporates the ices; or through non-thermal desorption mechanisms, such as photodesorption, when a single far-UV photon releases only a few molecules from the ices. The first mechanism dominates in hot cores, hot corinos and strongly UV-illuminated PDRs, while the second dominates in colder regions, such as low UV-field PDRs. This is the case of the Horsehead were dust temperatures are approximately eual to 20-30 K, and therefore offers a clean environment to investigate the role of photodesorption. We have carried out an unbiased spectral line survey at 3, 2 and 1mm with the IRAM-30m telescope in the Horsehead nebula, with an unprecedented combination of bandwidth, high spectral resolution and sensitivity. Two positions were observed: the warm PDR and a cold condensation shielded from the UV field (dense core), located just behind the PDR edge. We summarize our recently published results from this survey and present the first detection of the complex organic molecules HCOOH, CH2CO, CH3CHO and CH3CCH in a PDR. These species together with CH3CN present enhanced abundances in the PDR compared to the dense core. This suggests that photodesorption is an efficient mechanism to release complex molecules into the gas-phase in far-UV illuminated regions.

Revised spectroscopic parameters of SH(+) from ALMA and IRAM 30m observations.

Hydrides represent the first steps of interstellar chemistry. Sulfanylium (SH(+)), in particular, is a key tracer of energetic processes. We used ALMA and the IRAM 30 m telescope to search for the lowest frequency rotational lines of SH(+) toward the Orion Bar, the prototypical photo-dissociation region illuminated by a strong UV radiation field. On the basis of previous Herschel/HIFI observations of SH(+), we expected to detect emission of the two SH(+) hyperfine structure (HFS) components of the NJ = 10-01 fine structure (FS) component near 346 GHz. While we did not observe any lines at the frequencies predicted from laboratory data, we detected two emission lines, each ~15 MHz above the SH(+) predictions and with relative intensities and HFS splitting expected for SH(+). The rest frequencies of the two newly detected lines are more compatible with the remainder of the SH(+) laboratory data than the single line measured in the laboratory near 346 GHz and previously attributed to SH(+). Therefore, we assign these new features to the two SH(+) HFS components of the NJ = 10-01 FS component and re-determine its spectroscopic parameters, which will be useful for future observations of SH(+), in particular if its lowest frequency FS components are studied. Our observations demonstrate the suitability of these lines for SH(+) searches at frequencies easily accessible from the ground.