Rotational energy transfer in collisions between CO(X¹Σ⁺, v=2, J=0, 1,4, and 6) and He at temperatures from 294 to 15 K

Infrared-vacuum ultraviolet double resonance experiments have been implemented in the ultracold environment provided by a Cinétique de Réaction en Ecoulement Supersonique Uniforme apparatus. With this technique rate coefficients of two kinds have been measured for rotational energy transfer in collisions between CO and He: (a) those for total removal from the selected rotational states J = 0, 1, 4, and 6 in the vibronic state X 1+, v = 2, and (b) those for transfer between selected initial and specific final states. Using different Laval nozzles, results have been obtained at several different temperatures: 294, 149, 63, 27, and 15 K. The thermally averaged cross sections for total removal by collisions with He show only slight variations both with initial rotational state and with temperature. The variation of state-to-state rate coefficients with J show several general features: (i) a decrease with increasing J; (ii) a propensity to favor odd J over even J; and (iii) at lower temperatures, the distribution of rate coefficients against J becomes narrower, and decreases in J are increasingly favored over increases in J, a preference which is most strongly seen for higher initial values of J. The results are shown to be in remarkably good agreement with those obtained in ab initio scattering calculations by Dalgarno and co-workers [Astrophys. J. 571, 1015 (2002)]

Understanding the Chemical Complexity in Circumstellar Envelopes of C-rich AGB Stars: the Case of IRC +10216

The circumstellar envelopes of carbon-rich AGB stars show a chemical complexity that is exemplified by the prototypical object IRC +10216, in which about 60 different molecules have been detected to date. Most of these species are carbon chains of the type CnH, CnH2, CnN, HCnN. We present the detection of new species (CH2CHCN, CH2CN, H2CS, CH3CCH and C3O) achieved thanks to the systematic observation of the full 3 mm window with the IRAM 30m telescope plus some ARO 12m observations. All these species, known to exist in the interstellar medium, are detected for the first time in a circumstellar envelope around an AGB star. These five molecules are most likely formed in the outer expanding envelope rather than in the stellar photosphere. A pure gas phase chemical model of the circumstellar envelope is reasonably successful in explaining the derived abundances, and additionally allows to elucidate the chemical formation routes and to predict the spatial distribution of the detected species.Comment: 4 pages, 4 figures; to appear in Astrophysics and Space Science, special issue of "Science with ALMA: a new era for Astrophysics" conference, November, 13-17 2006, ed. R. Bachille

Rate Constants and Branching Ratios for the Reaction of CH Radicals with NH3 : A Combined Experimental and Theoretical Study

International audienceRate Constants and Branching Ratios for the Reaction of CH Radicals with NH3 : A Combined Experimental and Theoretical Stud

Low temperature rate coefficients for the reactions of CN and C₂H radicals with allene (CH₂=C=CH₂) and methyl acetylene (CH₃C=CH)

Using a continuous flow CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus, rate coefficients have been measured for the reactions of the cyanogen (CN) and ethynyl (C2H) radicals with allene (CH2=C-CH2) and methyl acetylene (CH3C=CH) at temperatures from 295 down to 15 K for the reactions of CN and down to 63 K for those Of C2H. All four reactions occur at rates close to the collision-determined limit. The results are compared with those obtained earlier for the reactions of other alkenes and alkynes, and, in the accompanying Letter by Vakhtin et al., with results for C2H + CH2=C=CH2 and C2H + CH3C=CH obtained at 103 K using a pulsed Laval apparatus. The implications of these latest results for the chemistry of interstellar clouds and planetary atmospheres are discussed

Kinetics of the radical-radical reaction, O(triplet P,J + OH(X doublet pi omega) - O2 + H, at temperatures down to 39 K

The kinetics of the reaction between O atoms and OH radicals, both in their electronic ground state, have been investigated at temperatures down to ca. 39 K. The experiments employed a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme) apparatus to attain low temperatures. Both reagents were created using pulsed laser photolysis at 157.6 nm of mixtures containing H2O and O2 diluted in N2 carrier gas. OH radicals were formed by both direct photolysis of H2O and the reaction between O(1D) atoms and H2O. O(3P) atoms were formed both as a direct product of O2 photolysis and by the rapid quenching of O(1D) atoms formed in that photolysis by N2 and O2. The rates of removal of OH radicals were observed by laser-induced fluorescence, and concentrations of O atoms were estimated from a knowledge of the absorption cross-section for O2 at 157.6 nm and of the measured fluence from the F2 laser at this wavelength. To obtain a best estimate of the rate constants for the O + OH reaction, we had to correct the raw experimental data for the following: (a) the decrease in the laser fluence along the jet due to the absorption by O2 in the gas mixture, (b) the increase in temperature, and consequent decrease in gas density, as a result of energy released in the photochemical and chemical processes that occurred, and (c) the formation of OH(v = 0) as a result of relaxation, particularly by O2, of OH radicals formed in levels v > 0. Once these corrections were made, the rate constant for reaction between OH and O(3P) atoms showed little variation in the temperature range of 142 to 39 K and had a value of (3.5 ± 1.0) × 10-11 cm3 molecule-1 s-1. It is recommended that this value is used in future chemical models of dense interstellar clouds