An Experimental and Theoretical Investigation of the Gas-Phase C(3P) + N2O Reaction. Low Temperature Rate Constants and Astrochemical Implications.

The reaction between atomic carbon in its ground electronic state, C(3P), and nitrous oxide, N2O, has been studied below room temperature due to its potential importance for astrochemistry, with both species considered to be present at high abundance levels in a range of interstellar environments. On the experimental side, we measured rate constants for this reaction over the 50-296 K range using a continuous supersonic flow reactor. C(3P) atoms were generated by the pulsed photolysis of carbon tetrabromide at 266 nm and were detected by pulsed laser-induced fluorescence at 115.8 nm. Additional measurements allowing the major product channels to be elucidated were also performed. On the theoretical side, statistical rate theory was used to calculate low temperature rate constants. These calculations employed the results of new electronic structure calculations of the 3A″ potential energy surface of CNNO and provided a basis to extrapolate the measured rate constants to lower temperatures and pressures. The rate constant was found to increase monotonically as the temperature falls (kC(3P)+N2O (296 K) = (3.4 ± 0.3) × 10-11 cm3 s-1), reaching a value of kC(3P)+N2O (50 K) = (7.9 ± 0.8) × 10-11 cm3 s-1 at 50 K. As current astrochemical models do not include the C + N2O reaction, we tested the influence of this process on interstellar N2O and other related species using a gas-grain model of dense interstellar clouds. These simulations predict that N2O abundances decrease significantly at intermediate times (103 - 105 years) when gas-phase C(3P) abundances are high.

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.

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.

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.

Low temperature rate constants for the N(4S) + CH(X2Πr) reaction. Implications for N2 formation cycles in dense interstellar clouds.

Rate constants for the potentially important interstellar N((4)S) + CH(X(2)Πr) reaction have been measured in a continuous supersonic flow reactor over the range 56 K ≤T≤ 296 K using the relative rate technique employing both the N((4)S) + OH(X(2)Πi) and N((4)S) + CN(X(2)Σ(+)) reactions as references. Excess concentrations of atomic nitrogen were produced by the microwave discharge method upstream of the Laval nozzle and CH and OH radicals were created by the in situ pulsed laser photolysis of suitable precursor molecules. In parallel, quantum dynamics calculations of the title reaction have been performed based on accurate global potential energy surfaces for the 1(3)A' and 1(3)A'' states of HCN and HNC, brought about through a hierarchical construction scheme. Both adiabatic potential energy surfaces are barrierless, each one having two deep potential wells suggesting that this reaction is dominated by a complex-forming mechanism. The experimental and theoretical work are in excellent agreement, predicting a positive temperature dependence of the rate constant, in contrast to earlier experimental work at low temperature. The effects of the new low temperature rate constants on interstellar N2 formation are tested using a dense cloud model, yielding N2 abundances 10-20% lower than previously predicted.

Elemental nitrogen partitioning in dense interstellar clouds.

Many chemical models of dense interstellar clouds predict that the majority of gas-phase elemental nitrogen should be present as N(2), with an abundance approximately five orders of magnitude less than that of hydrogen. As a homonuclear diatomic molecule, N(2) is difficult to detect spectroscopically through infrared or millimeter-wavelength transitions. Therefore, its abundance is often inferred indirectly through its reaction product N(2)H(+). Two main formation mechanisms, each involving two radical-radical reactions, are the source of N(2) in such environments. Here we report measurements of the low temperature rate constants for one of these processes, the N + CN reaction, down to 56 K. The measured rate constants for this reaction, and those recently determined for two other reactions implicated in N(2) formation, are tested using a gas-grain model employing a critically evaluated chemical network. We show that the amount of interstellar nitrogen present as N(2) depends on the competition between its gas-phase formation and the depletion of atomic nitrogen onto grains. As the reactions controlling N(2) formation are inefficient, we argue that N(2) does not represent the main reservoir species for interstellar nitrogen. Instead, elevated abundances of more labile forms of nitrogen such as NH(3) should be present on interstellar ices, promoting the eventual formation of nitrogen-bearing organic molecules.