Context. Complex organic molecules (COMs) have long been detected in the interstellar medium, especially in hot cores and in the hot corinos of low-mass protostars. Their formation routes however remain uncertain. Both warm gas-phase reactions and warm grain-surface reactions have been invoked to account for their presence in low-mass protostars. In this latter scheme, COMs result from radical-radical reactions on the grains as radicals become mobile when the nascent protostar warms up its surroundings and the resulting molecules are subsequently desorbed into the gas phase at higher temperatures. Aims. Prestellar cores are the direct precursors of low-mass protostars and offer a unique opportunity to study the formation of COMs before the warm-up phase. Their very low temperatures (≤10 K) and the absence of any heating source or outflow exclude any efficient warm gas phase or warm dust chemistry, so that the presence of COMs in prestellar cores would have to originate from non-thermal chemical processes. Methods. We used the IRAM 30 m telescope to look for four O-bearing COMs (acetaldehyde CH 3 CHO, dimethyl ether CH 3 OCH 3 , methyl formate CH 3 OCHO, and ketene CH 2 CO) in the prestellar core L1689B. Results. We report the unambiguous detection of all four molecules in the cold gas phase of L1689B. These detections support the role played by non-thermal (possibly photolytic) processes in COM formation and desorption, though the presence of dimethyl ether is so far unexplained by current grain formation scenarios. The data show univocally that COM synthesis has already started at the prestellar stage and suggests at least part of the COMs detected in hot corinos have a prestellar origin.

Chemical models used to study the chemical composition of the gas and the ices in the interstellar medium are based on a network of chemical reactions and associated rate coefficients. These reactions and rate coefficients are partially compiled from data in the literature, when available. We present in this paper kida.uva.2014, a new updated version of the kida.uva public gas-phase network first released in 2012. In addition to a description of the many specific updates, we illustrate changes in the predicted abundances of molecules for cold dense cloud conditions as compared with the results of the previous version of our network, kida.uva.2011.

Context. Water is a primordial species in the emergence of life, and comets may have brought a large fraction to Earth to form the oceans. To understand the evolution of water from the first stages of star formation to the formation of planets and comets, the HDO/H 2 O ratio is a powerful diagnostic. Aims. Our aim is to determine precisely the abundance distribution of HDO towards the low-mass protostar IRAS 16293-2422 and learn more about the water formation mechanisms by determining the HDO/H 2 O abundance ratio. Results. It is the first time that so many HDO and H 182 O transitions have been detected towards the same source with high spectral resolution. We derive an inner HDO abundance (T ≥ 100 K) of about 1.7 × 10 −7 and an outer HDO abundance (T < 100 K) of about 8 × 10 −11 . To reproduce the HDO absorption lines observed at 894 and 465 GHz, it is necessary to add an absorbing layer in front of the envelope. It may correspond to a water-rich layer created by the photodesorption of the ices at the edges of the molecular cloud. At a 3σ uncertainty, the HDO/H 2 O ratio is 1.4-5.8% in the hot corino, whereas it is 0.2-2.2% in the outer envelope. It is estimated at ∼4.8% in the added absorbing layer. Conclusions. Although it is clearly higher than the cosmic D/H abundance, the HDO/H 2 O ratio remains lower than the D/H ratio derived for other deuterated molecules observed in the same source. The similarity of the ratios derived in the hot corino and in the added absorbing layer suggests that water formed before the gravitational collapse of the protostar, contrary to formaldehyde and methanol, which formed later once the CO molecules had depleted on the grains.

The potential energy surface of H(2)O-H(2) is of great importance for quantum chemistry as a test case for H(2)O-molecule interactions. It is also required for a detailed understanding of important astrophysical processes, namely, the collisional excitation of water, including the pumping of water masers and the formation of molecular hydrogen on icy interstellar dust grains. We have calculated the interaction for H(2)O-H(2) by performing both rigid-rotor (five-dimensional) and non-rigid-rotor (nine-dimensional) calculations using the coupled-cluster theory at the level of singles and doubles with perturbative corrections for triple excitations [CCSD(T)] with moderately large but thoroughly selected basis set. The resulting surface was further calibrated using high precision explicitly correlated CCSD(T)-R12 calculations on a subset of the rigid-rotor intermolecular geometries. The vibrationally averaged potential is presented in some details and is compared with the most recent rigid-rotor calculations. We explain, in particular, as to why vibrationally averaged rigid-rotor geometries are a better choice than equilibrium geometries. Our fit of the vibrationally averaged surface provides for the first time an accuracy of approximately 3 cm(-1) in the van der Waals minimum region of the interaction. The overall accuracy of the nine-dimensional surface and fit is lower but remains of the order of 3%-4% of the anisotropy in the domain spanned by the vibrational functions.

The internal energy available in vibrationally excited H 2 molecules can be used to overcome or diminish the activation barrier of various chemical reactions of interest for molecular astrophysics. In this article we investigate in detail the impact on the chemical composition of interstellar clouds of the reactions of vibrationally excited H 2 with C + , He + , O, OH, and CN, based on the available chemical kinetics data. It is found that the reaction of H 2 (v > 0) and C + has a profound impact on the abundances of some molecules, especially CH + , which is a direct product and is readily formed in astronomical regions with fractional abundances of vibrationally excited H 2 , relative to ground state H 2 , in excess of ∼ 10 −6 , independently of whether the gas is hot or not. The effects of these reactions on the chemical composition of the diffuse clouds ζ Oph and HD 34078, the dense PDR Orion Bar, the planetary nebula NGC 7027, and the circumstellar disk around the B9 star HD 176386 are investigated through PDR models. We find that formation of CH + is especially favored in dense and highly FUV illuminated regions such as the Orion Bar and the planetary nebula NGC 7027, where column densities in excess of 10 13 cm −2 are predicted. In diffuse clouds, however, this mechanism is found to be not efficient enough to form CH + with a column density close to the values derived from astronomical observations.

Context. The interpretation of water line emission from existing observations and future HIFI/Herschel data requires a detailed knowledge of collisional rate coefficients. Among all relevant collisional mechanisms, the rotational (de)excitation of H 2 O by H 2 molecules is the process of most interest in interstellar space. Aims. To determine rate coefficients for rotational de-excitation among the lowest 45 para and 45 ortho rotational levels of H 2 O colliding with both para and ortho-H 2 in the temperature range 20−2000 K. Methods. Rate coefficients are calculated on a recent high-accuracy H 2 O−H 2 potential energy surface using quasi-classical trajectory calculations. Trajectories are sampled by a canonical Monte-Carlo procedure. H 2 molecules are assumed to be rotationally thermalized at the kinetic temperature. Results. By comparison with quantum calculations available for low lying levels, classical rates are found to be accurate within a factor of 1−3 for the dominant transitions, that is those with rates larger than a few 10 −12 cm 3 s −1 . Large velocity gradient modelling shows that the new rates have a significant impact on emission line fluxes and that they should be adopted in any detailed population model of water in warm and hot environments.

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Integral cross-section measurements for the system water-H(2) in molecular-beam scattering experiments are reported. Their analysis demonstrates that the average attractive component of the water-H(2) intermolecular potential in the well region is about 30% stronger than dispersion and induction forces would imply. An extensive and detailed theoretical analysis of the electron charge displacement accompanying the interaction, over several crucial sections of the potential energy surface (PES), shows that water-H(2) interaction is accompanied by charge transfer (CT) and that the observed stabilization energy correlates quantitatively with CT magnitude at all distances. Based on the experimentally determined potential and the calculated CT, a general theoretical model is devised which reproduces very accurately PES sections obtained at the CCSD(T) level with large basis sets. The energy stabilization associated with CT is calculated to be 2.5 eV per electron transferred. Thus, CT is shown to be a significant, strongly stereospecific component of the interaction, with water functioning as electron donor or acceptor in different orientations. The general relevance of these findings for water's chemistry is discussed.