New kinetic data and product distributions have been obtained using the experimental CRESU technique combined with a theoretical analysis of the reaction mechanism. The astrophysical implications of fast CH3O and CH2OH formation are discussed.

Chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T∼10-100K). Scarce kinetic information is currently available for this kind of reactions at T<200 K. In this work we use the CRESU (, which means Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients () of the gas-phase OH+HCO reaction between 22 and 107 K. values greatly increase from 2.1×10 cm s at 107 K to 1.2×10 cm s at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and potential energy surface, recently developed which generates highly accurate potential and includes long range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+HCO reaction. In order to revisit the chemistry of HCO in cold dense clouds, is reasonably extrapolated from the experimental results at 10K (2.6×10 cm s). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 10-10 yrs. The different sources of production of HCO are presented and the uncertainties in the chemical networks discussed. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. The present reaction is shown to account for a few percent of the total HCO production rate. Extensions to photodissociation regions and diffuse clouds environments are also commented.

Ethanol, CHCHOH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CHCHOH (k(T)) between 21 and 107 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(107 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10 (T/300 K) cm molecule s. In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (∼10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10 cm molecule s at 100 K and around 1 × 10 cm molecule s at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

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Pure acetonitrile (CH3CN) and mixed CO:CH3CN and H2O:CH3CN ices have been irradiated at 15 K with vacuum ultraviolet (VUV) photons in the 7–13.6 eV range using synchrotron radiation. VUV photodesorption yields of CH3CN and of photoproducts have been derived as a function of the incident photon energy. The coadsorption of CH3CN with CO and H2O molecules, which are expected to be among the main constituents of interstellar ices, is found to have no significant influence on the VUV photodesorption spectra of CH3CN, CHCN•, HCN, CN•, and CH3•. Contrary to what has generally been evidenced for most of the condensed molecules, these findings point toward a desorption process for which the CH3CN molecule that absorbs the VUV photon is the one desorbing. It can be ejected in the gas phase as intact CH3CN or in the form of its photodissociation fragments. Astrophysical VUV photodesorption yields, applicable to different locations, are derived and can be incorporated into astrochemical modeling. They vary from 0.67(± 0.33) × 10−5 to 2.0(± 1.0) × 10−5 molecule photon−1 for CH3CN depending on the region considered, which is high compared to other organic molecules such as methanol. These results could explain the multiple detections of gas-phase CH3CN in different regions of the interstellar medium and are well correlated to astrophysical observations of the Horsehead nebula and of protoplanetary disks (such as TW Hya and HD 163296).

Methanol (CH3OH) and hydroxyl (OH) radicals are two species abundant in cold and dense molecular clouds which are important for the chemistry of the interstellar medium (ISM). CH3OH is a well-known starting point for the formation of more complex organic molecules (COMs) in these molecular clouds. Thus, the reactivity of CH3OH in the gas-phase with OH may play a crucial role in the formation of species as complex as prebiotic molecules in the ISM and reliable rate coefficients should be used in astrochemical models describing low temperature reaction networks.

The rate coefficients, k(T= 11.7 – 64.4 K), for the gas-phase reaction between OH radicals and acetone, CH3C(O) CH3, have been measured using the pulsed CRESU (French acronym for Reaction Kinetics in a Uniform Supersonic Flow) technique, the most suitable one to cool down gases below the freezing point without gas condensation. The experimental k(T) was found to increase as temperature was lowered and is several orders of magnitude higher for low temperature than k(300 K). No pressure dependence of k(20 K) and k(64 K) was observed, while k(50 K) at the largest gas density is twice higher than the average values found at lower gas densities. The obtained values of k(11.7 K) and k(21.1 K) were 2.45’10-10 and 1.39’10-10 cm3 molecule-1 s-1, respectively.