Effect of temperature on the gas-phase reaction of CH3CN with OH radicals: experimental (T = 11.7-177.5 K) and computational (T = 10-400 K) kinetic study.

Acetonitrile (CH3CN) is present in the interstellar medium (ISM) in a variety of environments. However, at the ultracold temperatures of the ISM, radical-molecule reactions are not widely investigated because of the experimental handicap of getting organic molecules in the gas phase by conventional techniques. The CRESU (French acronym for Reaction Kinetics in a Uniform Supersonic Flow) technique solves this problem. For this reason, we present in this work the kinetic study of the gas-phase reaction of CH3CN with one of the most ubiquitous radicals, the hydroxyl (OH) radical, as a function of temperature (11.7-177.5 K). The kinetic technique employed to investigate the CH3CN + OH reaction was the pulsed laser photolysis-laser induced fluorescence. The rate coefficient for this reaction k(T) has been observed to drastically increase from 177.5 K to 107.0 K (about 2 orders of magnitude), while the increase in k(T) from 107.0 K to 11.7 K was milder (around 4 times). The temperature dependent expressions for k(T) are provided in the two distinct T-ranges, excluding the upper limit obtained for k(177.5 K): In addition, the rate coefficients estimated by the canonical competitive unified statistical (CCUS) theory show a similar behaviour to the experimental results, when evaluated within the high-pressure limit. This is consistent with the experimentally observed independence of k(T) with total gas density at selected temperatures. Astrochemical networks, such as the KIDA database or UMIST, do not include the CH3CN + OH reaction as a potential depletion process for acetonitrile in the ISM because the current studies predict very low rate coefficients at IS temperatures. According to the model (T = 10 K), the impact of the titled reaction on the abundances of CH3CN appears to be negligible in dark molecular clouds of the ISM (∼1% of the total depletion reactions included in UMIST network). With respect to the potential formation of the CH2CN radical in those environments, even in the most favourable scenario, where this radical could be formed in a 100% yield from the CH3CN + OH reaction, this route would only contribute around 2% to the current assumed formation routes by the UMIST network.

Searches for bridged bicyclic molecules in space-norbornadiene and its cyano derivatives.

The norbornadiene (NBD) molecule, C7H8, owes its fame to its remarkable photoswitching properties that are promising for molecular solar-thermal energy storage systems. Besides this photochemical interest, NBD is a rather unreactive species within astrophysical conditions and it should exhibit high photostability, properties that might also position this molecule as an important constituent of the interstellar medium (ISM)-especially in environments that are well shielded from short-wavelength radiation, such as dense molecular clouds. It is thus conceivable that, once formed, NBD can survive in dense molecular clouds and act as a carbon sink. Following the recent interstellar detections of large hydrocarbons, including several cyano-containing ones, in the dense molecular cloud TMC-1, it is thus logical to consider searching for NBD-which presents a shallow but non-zero permanent electric dipole moment (0.06 D)-as well as for its mono- and dicyano-substituted compounds, referred to as CN-NBD and DCN-NBD, respectively. The pure rotational spectra of NBD, CN-NBD, and DCN-NBD have been measured at 300 K in the 75-110 GHz range using a chirped-pulse Fourier-transform millimetre-wave spectrometer. Of the three species, only NBD was previously studied at high resolution in the microwave domain. From the present measurements, the derived spectroscopic constants enable prediction of the spectra of all three species at various rotational temperatures (up to 300 K) in the spectral range mapped at high resolution by current radio observatories. Unsuccessful searches for these molecules were conducted toward TMC-1 using the QUIJOTE survey, carried out at the Yebes telescope, allowing derivation of the upper limits to the column densities of 1.6 × 1014 cm-2, 4.9 × 1010 cm-2, and 2.9 × 1010 cm-2 for NBD, CN-NBD, and DCN-NBD, respectively. Using CN-NBD and cyano-indene as proxies for the corresponding bare hydrocarbons, this indicates that-if present in TMC-1-NBD would be at least four times less abundant than indene.

Silicon and Hydrogen Chemistry under Laboratory Conditions Mimicking the Atmosphere of Evolved Stars.

Silicon is present in interstellar dust grains, meteorites and asteroids, and to date thirteen silicon-bearing molecules have been detected in the gas-phase towards late-type stars or molecular clouds, including silane and silane derivatives. In this work, we have experimentally studied the interaction between atomic silicon and hydrogen under physical conditions mimicking those at the atmosphere of evolved stars. We have found that the chemistry of Si, H and H2 efficiently produces silane (SiH4), disilane (Si2H6) and amorphous hydrogenated silicon (a-Si:H) grains. Silane has been definitely detected towards the carbon-rich star IRC+10216, while disilane has not been detected in space yet. Thus, based on our results, we propose that gas-phase reactions of atomic Si with H and H2 are a plausible source of silane in C-rich AGBs, although its contribution to the total SiH4 abundance may be low in comparison with the suggested formation route by catalytic reactions on the surface of dust grains. In addition, the produced a-Si:H dust analogs decompose into SiH4 and Si2H6 at temperatures above 500 K, suggesting an additional mechanism of formation of these species in envelopes around evolved stars. We have also found that the exposure of these dust analogs to water vapor leads to the incorporation of oxygen into Si-O-Si and Si-OH groups at the expense of SiH moieties, which implies that, if this type of grains are present in the interstellar medium, they will be probably processed into silicates through the interaction with water ices covering the surface of dust grains.

The Chemistry of Cosmic Dust Analogues from C, C2, and C2H2 in C-Rich Circumstellar Envelopes.

Interstellar carbonaceous dust is mainly formed in the innermost regions of circumstellar envelopes around carbon-rich asymptotic giant branch (AGB) stars. In these highly chemically stratified regions, atomic and diatomic carbon, along with acetylene are the most abundant species after H2 and CO. In a previous study, we addressed the chemistry of carbon (C and C2) with H2 showing that acetylene and aliphatic species form efficiently in the dust formation region of carbon-rich AGBs whereas aromatics do not. Still, acetylene is known to be a key ingredient in the formation of linear polyacetylenic chains, benzene and polycyclic aromatic hydrocarbons (PAHs), as shown by previous experiments. However, these experiments have not considered the chemistry of carbon (C and C2) with C2H2. In this work, by employing a sufficient amount of acetylene, we investigate its gas-phase interaction with atomic and diatomic carbon. We show that the chemistry involved produces linear polyacetylenic chains, benzene and other PAHs, which are observed with high abundances in the early evolutionary phase of planetary nebulae. More importantly, we have found a non-negligible amount of pure and hydrogenated carbon clusters as well as aromatics with aliphatic substitutions, both being a direct consequence of the addition of atomic carbon. The incorporation of alkyl substituents into aromatics can be rationalized by a mechanism involving hydrogen abstraction followed by methyl addition. All the species detected in gas phase are incorporated into the nanometric sized dust analogues, which consist of a complex mixture of sp, sp2 and sp3 hydrocarbons with amorphous morphology.

Gas-phase kinetics of CH3CHO with OH radicals between 11.7 and 177.5 K.

Gas-phase reactions in the interstellar medium (ISM) are a source of molecules in this environment. The knowledge of the rate coefficient for neutral-neutral reactions as a function of temperature, k(T), is essential to improve astrochemical models. In this work, we have experimentally measured k(T) for the reaction between the OH radical and acetaldehyde, both present in many sources of the ISM. Laser techniques coupled to a CRESU system were used to perform the kinetic measurements. The obtained modified Arrhenius equation is k(T = 11.7-177.5 K) = (1.2 ± 0.2) × 10-11 (T/300 K)-(1.8±0.1) exp-{(28.7 ± 2.5)/T} cm3 molecule-1 s-1. The k(T) value of the title reaction has been measured for the first time below 60 K. No pressure dependence of k(T) was observed at ca. 21, 50, 64 and 106 K. Finally, a pure gas-phase model indicates that the title reaction could become the main CH3CO formation pathway in dark molecular clouds, assuming that CH3CO is the main reaction product at 10 K.

Prevalence of non-aromatic carbonaceous molecules in the inner regions of circumstellar envelopes.

Evolved stars are a foundry of chemical complexity, gas and dust that provides the building blocks of planets and life, and dust nucleation first occurs in their photosphere. Despite their importance, the circumstellar regions enveloping these stars remain hidden to many observations, thus dust formation processes are still poorly understood. Laboratory astrophysics provides complementary routes to unveil these chemical processes, but most experiments rely on combustion or plasma decomposition of molecular precursors under physical conditions far removed from those in space. We have built an ultra-high vacuum machine combining atomic gas aggregation with advanced in-situ characterization techniques to reproduce and characterize the bottom-up dust formation process. We show that carbonaceous dust analogues formed from low-pressure gas-phase condensation of C atoms in a hydrogen atmosphere, in a C/H2 ratio similar to that reported for evolved stars, leads to the formation of amorphous C nanograins and aliphatic C-clusters. Aromatic species or fullerenes do not form effectively under these conditions, raising implications for the revision of the chemical mechanisms taking place in circumstellar envelopes.

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.

Gas Accretion within the Dust Cavity in AB Aur.

AB Aur is a Herbig Ae star hosting a well-known transitional disk. Because of its proximity and low inclination angle, it is an excellent object to study planet formation. Our goal is to investigate the chemistry and dynamics of the molecular gas component in the AB Aur disk, and its relation with the prominent horseshoe shape observed in continuum mm emission. We used the NOEMA interferometer to map with high angular resolution the J = 3-2 lines of HCO+ and HCN. By combining both, we can gain insight into the AB Aur disk structure. Chemical segregation is observed in the AB Aur disk: HCO+ shows intense emission toward the star position, at least one bright molecular bridge within the dust cavity, and ring-like emission at larger radii, while HCN is only detected in an annular ring that is coincident with the dust ring and presents an intense peak close to the dust trap. We use HCO+ to investigate the gas dynamics inside the cavity. The observed bright HCO+ bridge connects the compact central source with the outer dusty ring. This bridge can be interpreted as an accretion flow from the outer ring to the inner disk/jet system proving gas accretion through the cavity.

Hints of the existence of C-rich massive evolved stars.

We aim at studying the properties of a particular type of evolved stars, the C-rich evolved stars with high expansion velocities. For this purpose we have focused on the two best studied objects within this group, IRC +10401 and AFGL 2233. We focused on determining their luminosity by studying their spectral energy distribution. Also we have obtained single-dish line profiles and interferometric maps of the CO J=1-0 and J=2-1emission lines for both objects. We have modeled this emission using a LVG radiative transfer code to determine the kinetic temperature and density profiles of the gas ejected by these stars. We have found that the luminosities obtained for these objects (log(L/L ⊙) = 4.1 & 5.4) locate them in the domain of the massive Asymptotic Giant Branch stars (AGBs) and the Red Supergiant stars (RSGs). In addition, the mass-loss rates obtained (1.5 × 10-5 - 6 × 10-3 M ⊙ yr-1) suggest that while IRC+10401 might be an AGB star, AFGL 2233 could be a RSG star. All these results, together with those from previous works suggest that both objects are massive objects, IRC +10401 a massive evolved star with M init ~ 5 - 9M ⊙ which could correspond to an AGB or a RSG and AFGL 2233 a RSG with M init ~ 20M ⊙, which would confirm the existence of massive C-rich evolved stars. Two scenarios are proposed to form these types of objects. The first one capable of producing high mass AGB stars up to ~ 8M ⊙ and a second one capable of forming C-rich RSGs as AFGL 2233.

The chemistry of disks around T Tauri and Herbig Ae/Be stars.

CONTEXT: Infrared and (sub-)mm observations of disks around T Tauri and Herbig Ae/Be stars point to a chemical differentiation between both types of disks, with a lower detection rate of molecules in disks around hotter stars. AIMS: To investigate the underlying causes of the chemical differentiation indicated by observations we perform a comparative study of the chemistry of T Tauri and Herbig Ae/Be disks. This is one of the first studies to compare chemistry in the outer regions of these two types of disks. METHODS: We developed a model to compute the chemical composition of a generic protoplanetary disk, with particular attention to the photochemistry, and applied it to a T Tauri and a Herbig Ae/Be disk. We compiled cross sections and computed photodissociation and photoionization rates at each location in the disk by solving the FUV radiative transfer in a 1+1D approach using the Meudon PDR code and adopting observed stellar spectra. RESULTS: The warmer disk temperatures and higher ultraviolet flux of Herbig stars compared to T Tauri stars induce some differences in the disk chemistry. In the hot inner regions, H2O, and simple organic molecules like C2H2, HCN, and CH4 are predicted to be very abundant in T Tauri disks and even more in Herbig Ae/Be disks, in contrast with infrared observations that find a much lower detection rate of water and simple organics toward disks around hotter stars. In the outer regions, the model indicates that the molecules typically observed in disks, like HCN, CN, C2H, H2CO, CS, SO, and HCO+, do not have drastic abundance differences between T Tauri and Herbig Ae disks. Some species produced under the action of photochemistry, like C2H and CN, are predicted to have slightly lower abundances around Herbig Ae stars due to a narrowing of the photochemically active layer. Observations indeed suggest that these radicals are somewhat less abundant in Herbig Ae disks, although in any case the inferred abundance differences are small, of a factor of a few at most. A clear chemical differentiation between both types of disks concerns ices. Owing to the warmer temperatures of Herbig Ae disks, one expects snowlines lying farther away from the star and a lower mass of ices compared to T Tauri disks. CONCLUSIONS: The global chemical behavior of T Tauri and Herbig Ae/Be disks is quite similar. The main differences are driven by the warmer temperatures of the latter, which result in a larger reservoir or water and simple organics in the inner regions and a lower mass of ices in the outer disk.

Formation and Destruction of SiS in Space.

The presence of SiS in space seems to be restricted to a few selected types of astronomical environments. It is long known to be present in circumstellar envelopes around evolved stars and it has also been detected in a handful of star-forming regions with evidence of outflows, like Sgr B2, Orion KL and more recently L1157-B1. The kinetics of reactions involving SiS is very poorly known and here we revisit the chemistry of SiS in space by studying some potentially important reactions of formation and destruction of this molecule. We calculated ab initio potential energy surfaces of the SiOS system and computed rate coefficients in the temperature range 50-2500 K for the reaction of destruction of SiS, in collisions with atomic O, and of its formation, through the reaction between Si and SO. We find that both reactions are rapid, with rate coefficients of a few times 10-10 cm3 s-1, almost independent of temperature. In the reaction between Si and SO, SiO production is 5-7 times more efficient than SiS formation. The reaction of SiS with O atoms can play an important role in destroying SiS in envelopes around evolved stars. We built a simple chemical model of a postshock gas to study the chemistry of SiS in protostellar outflows and we found that SiS forms with a lower abundance and later than SiO, that SiS is efficiently destroyed through reaction with O, and that the main SiS-forming reactions are Si + SO and Si + SO2.

Full dimensional potential energy surface and low temperature dynamics of the H2CO + OH → HCO + H2O reaction.

A new method is proposed to analytically represent the potential energy surface of reactions involving polyatomic molecules capable of accurately describing long-range interactions and saddle points, needed to describe low-temperature collisions. It is based on two terms, a reactive force field term and a many-body term. The reactive force field term accurately describes the fragments, long-range interactions among them and the saddle points for reactions. The many-body term increases the desired accuracy everywhere else. This method has been applied to the OH + H2CO → H2O + HCO reaction, giving a barrier of 27.4 meV. The simulated classical rate constants with this potential are in good agreement with recent experimental results [Ocaña et al., Astrophys. J., 2017, submitted], showing an important increase at temperatures below 100 K. The reaction mechanism is analyzed in detail here, and explains the observed behavior at low energy by the formation of long-lived collision complexes, with roaming trajectories, with a capture observed for very long impact parameters, >100 a.u., determined by the long-range dipole-dipole interaction.

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.

Probing the Cold Dust Emission in the AB Aur Disk: A Dust Trap in a Decaying Vortex?

One serious challenge for planet formation is the rapid inward drift of pebble-sized dust particles in protoplanetary disks. Dust trapping at local maxima in the disk gas pressure has received much theoretical attention but still lacks observational support. The cold dust emission in the AB Aur disk forms an asymmetric ring at a radius of about 120 au, which is suggestive of dust trapping in a gas vortex. We present high spatial resolution (0".58×0".78 ≈ 80×110 au) NOEMA observations of the 1.12 mm and 2.22 mm dust continuum emission from the AB Aur disk. Significant azimuthal variations of the flux ratio at both wavelengths indicate a size segregation of the large dust particles along the ring. Our continuum images also show that the intensity variations along the ring are smaller at 2.22 mm than at 1.12 mm, contrary to what dust trapping models with a gas vortex have predicted. Our two-fluid (gas+dust) hydrodynamical simulations demonstrate that this feature is well explained if the gas vortex has started to decay due to turbulent diffusion, and dust particles are thus losing the azimuthal trapping on different timescales depending on their size. The comparison between our observations and simulations allows us to constrain the size distribution and the total mass of solid particles in the ring, which we find to be of the order of 30 Earth masses, enough to form future rocky planets.

The Photodissociation of HCN and HNC: Effects on the HNC/HCN Abundance Ratio in the Interstellar Medium.

The impact of the photodissociation of HCN and HNC isomers is analyzed in different astrophysical environments. For this purpose, the individual photodissociation cross section of HCN and HNC isomers have been calculated in the 7-13.6 eV photon energy range for a temperature of 10 K. These calculations are based on the ab initio calculation of three-dimensional adiabatic potential energy surfaces of the 21 lower electronic states. The cross sections are then obtained using a quantum wave packet calculation of the rotational transitions needed to simulate a rotational temperature of 10 K. The cross section calculated for HCN shows significant differences with respect to the experimental one, and this is attributed to the need of considering non-adiabatic transitions. Ratios between the photodissociation rates of HCN and HNC under different ultraviolet radiation fields have been computed by renormalizing the rates to the experimental one. It is found that HNC is photodissociated faster than HCN by a factor of 2.2, for the local interstellar radiation field, and 9.2, for the solar radiation field at 1 au. We conclude that to properly describe the HNC/HCN abundance ratio in astronomical environments illuminated by an intense ultraviolet radiation field it is necessary to use different photodissociation rates for each of the two isomers, obtained by integrating the product of the photodissociation cross sections and ultraviolet radiation field over the relevant wavelength range.

Photodissociation of HCN and HNC isomers in the 7-10 eV energy range.

The ultraviolet photoabsorption spectra of the HCN and HNC isomers have been simulated in the 7-10 eV photon energy range. For this purpose, the three-dimensional adiabatic potential energy surfaces of the 7 lowest electronic states, and the corresponding transition dipole moments, have been calculated, at multireference configuration interaction level. The spectra are calculated with a quantum wave packet method on these adiabatic potential energy surfaces. The spectra for the 3 lower excited states, the dissociative electronic states, correspond essentially to predissociation peaks, most of them through tunneling on the same adiabatic state. The 3 higher electronic states are bound, hereafter electronic bound states, and their spectra consist of delta lines, in the adiabatic approximation. The radiative lifetime towards the ground electronic states of these bound states has been calculated, being longer than 10 ns in all cases, much longer that the characteristic predissociation lifetimes. The spectra of HCN is compared with the available experimental and previous theoretical simulations, while in the case of HNC there are no previous studies to our knowledge. The spectrum for HNC is considerably more intense than that of HCN in the 7-10 eV photon energy range, which points to a higher photodissociation rate for HNC, compared to HCN, in astrophysical environments illuminated by ultraviolet radiation.

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.

Exoplanetary Atmospheres-Chemistry, Formation Conditions, and Habitability.

Characterizing the atmospheres of extrasolar planets is the new frontier in exoplanetary science. The last two decades of exoplanet discoveries have revealed that exoplanets are very common and extremely diverse in their orbital and bulk properties. We now enter a new era as we begin to investigate the chemical diversity of exoplanets, their atmospheric and interior processes, and their formation conditions. Recent developments in the field have led to unprecedented advancements in our understanding of atmospheric chemistry of exoplanets and the implications for their formation conditions. We review these developments in the present work. We review in detail the theory of atmospheric chemistry in all classes of exoplanets discovered to date, from highly irradiated gas giants, ice giants, and super-Earths, to directly imaged giant planets at large orbital separations. We then review the observational detections of chemical species in exoplanetary atmospheres of these various types using different methods, including transit spectroscopy, Doppler spectroscopy, and direct imaging. In addition to chemical detections, we discuss the advances in determining chemical abundances in these atmospheres and how such abundances are being used to constrain exoplanetary formation conditions and migration mechanisms. Finally, we review recent theoretical work on the atmospheres of habitable exoplanets, followed by a discussion of future outlook of the field.

Discovery of interstellar ketenyl (HCCO), a surprisingly abundant radical.

We have conducted radioastronomical observations of 9 dark clouds with the IRAM 30m telescope. We present the first identification in space of the ketenyl radical (HCCO) toward the starless core Lupus-1A and the molecular cloud L483, and the detection of the related molecules ketene (H2CCO) and acetaldehyde (CH3CHO) in these two sources and 3 additional dark clouds. We also report the detection of the formyl radical (HCO) in the 9 targeted sources and of propylene (CH2CHCH3) in 4 of the observed sources, which extends significantly the number of dark clouds where these molecules are known to be present. We derive a beam-averaged column density of HCCO of ~ 5 × 1011 cm-2 in both Lupus-1A and L483, which means that the ketenyl radical is just ~10 times less abundant than ketene in these sources. The non-negligible abundance of HCCO found implies that there must be a powerful formation mechanism able to counterbalance the efficient destruction of this radical through reactions with neutral atoms. The column densities derived for HCO, (0.5-2.7) ×1012 cm-2, and CH2CHCH3, (1.9-4-2) ×1013 cm-2, are remarkably uniform across the sources where these species are detected, confirming their ubiquity in dark clouds. Gas phase chemical models of cold dark clouds can reproduce the observed abundances of HCO, but cannot explain the presence of HCCO in Lupus-1A and L483 and the high abundances derived for propylene. The chemistry of cold dark clouds needs to be revised in the light of these new observational results.