Interstellar deuterated ammonia: From NH3 to ND3

We use spectra and maps of NH2D, ND2H, and ND3, obtained with the CSO, IRAM 30m and Arecibo telescopes, to study deuteration processes in dense cores. The data include the first detection of the hyperfine structure of ND2H. The emission of ND2H and ND3 does not seem to peak at the positions of the embedded protostars, but instead at offset positions, where outflow interactions may occur. A constant ammonia fractionation ratio in star-forming regions is generally assumed to be consistent with an origin on dust grains. However, in the pre-stellar cores studied here, the fractionation varies significantly when going from NH3 to ND3. We present a steady state model of the gas-phase chemistry for these sources, which includes passive depletion onto dust grains and multiply saturated deuterated species up to five deuterium atoms (e.g. CD5+). The observed column density ratios of all four ammonia isotopologues are reproduced within a factor of 3 for a gas temperature of 10 K. We also predict that deuterium fractionation remains significant at temperatures up to 20 K. ND and NHD, which have rotational transitions in the submillimeter domain are predicted to be abundant.Comment: 14 pages, 12 figures, 12 table

WACCM-D Whole Atmosphere Community Climate Model with D-region ion chemistry

Energetic particle precipitation (EPP) and ion chemistry affect the neutral composition of the polar middle atmosphere. For example, production of odd nitrogen and odd hydrogen during strong events can decrease ozone by tens of percent. However, the standard ion chemistry parameterization used in atmospheric models neglects the effects on some important species, such as nitric acid. We present WACCM-D, a variant of the Whole Atmosphere Community Climate Model, which includes a set of lower ionosphere (D-region) chemistry: 307 reactions of 20 positive ions and 21 negative ions. We consider realistic ionization scenarios and compare the WACCM-D results to those from the Sodankylä Ion and Neutral Chemistry (SIC), a state-of-the-art 1-D model of the D-region chemistry. We show that WACCM-D produces well the main characteristics of the D-region ionosphere, as well as the overall proportion of important ion groups, in agreement with SIC. Comparison of ion concentrations shows that the WACCM-D bias is typically within ±10% or less below 70 km. At 70–90 km, when strong altitude gradients in ionization rates and/or ion concentrations exist, the bias can be larger for some groups but is still within tens of percent. Based on the good agreement overall and the fact that part of the differences are caused by different model setups, WACCM-D provides a state-of-the-art global representation of D-region ion chemistry and is therefore expected to improve EPP modeling considerably. These improvements are demonstrated in a companion paper by Andersson et al

Dissociative recombination and excitation of D₅⁺by collisions with low-energy electrons

We report results from high-resolution studies of D-5(+) cluster ion collisions with low-energy electrons performed in a heavy ion storage ring. Absolute dissociative recombination (DR) and dissociative excitation (DE) cross sections were determined for the energy range from 0.0005 to 20eV. The DR cross sections were exceedingly large at low energies, and DR resulted in efficient internal energy redistribution and pronounced fragmentation with two main product channels: D-2+3D (0.62 +/- 0.03) and 2D(2)+D (0.35 +/- 0.01). The DR and DE cross sections were comparable in the energy range from 0.2 to 20eV, which suggest that the two processes follow similar dynamics and are competing outcomes of the ion-electron interaction. A simple picture of the recombination process of D-5(+) which captures the essential physics is suggested. RAHAMSSON K, 1993, NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEA

Hot water from cold. The dissociative recombination of water cluster ions

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Dissociative recombination of water cluster ions with free electrons: Cross sections and branching ratios

Dissociative recombination (DR) of water cluster ions H+(H2O)n (n=4–6) with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, branching ratios have been determined for the dominating product channels and absolute DR cross sections have been measured in the energy range from 0.001 to 0.7 eV. Dissociative recombination is concluded to result in extensive fragmentation for all three cluster ions, and a maximum number of heavy oxygen-containing fragments is produced with a probability close to unity. The branching ratio results agree with earlier DR studies of smaller water cluster ions where the channel nH2O+H has been observed to dominate and where energy transfer to internal degrees of freedom has been concluded to be highly efficient. The absolute DR cross sections for H+(H2O)n (n=4–6) decrease monotonically with increasing energy with an energy dependence close to E−1 in the lower part of the energy range and a faster falloff at higher energies, in agreement with the behavior of other studied heavy ions. The cross section data have been used to calculate DR rate coefficients in the temperature range of 10–2000 K. The results from storage ring experiments with water cluster ions are concluded to partly confirm the earlier results from afterglow experiments. The DR rate coefficients for H+(H2O)n (n=1–6) are in general somewhat lower than reported from afterglow experiments. The rate coefficient tends to increase with increasing cluster size, but not in the monotonic way that has been reported from afterglow experiments. The needs for further experimental studies and for theoretical models that can be used to predict the DR rate of polyatomic ions are discussed