The dissociative recombination (DR) of N2H+ has been reinvestigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. Thermal rate coefficients for electron ...temperatures between 10 and 1000 K have been deduced. We show that electron recombination is expected to play an approximately equally important role as CO in the removal of N2H+ in dark interstellar clouds. We note that a deeper knowledge on the influence of the ions' rotational temperature in the DR of N2H+ would be helpful to set further constraints on the relative importance of the different destruction mechanisms for N2H+ in these environments. The branching fractions in the DR of N2H+ have been reinvestigated at similar to 0 eV relative kinetic energy, showing a strong dominance of the N-2 + H production channel (93(-2)(+4)%) with the rest leading to NH + N. These results are in good agreement with flowing afterglow experiments and in disagreement with an earlier measurement at CRYRING.
Branching ratios and absolute cross sections have been measured for the dissociative recombination of N2H+ using the CRYRING ion storage ring. It has been found that the channel N2H+ + e(-) --> ...N-2 + H accounts for only 36% of the total reaction and that the branching into the other exoergic pathway, N2H+ + e(-) --> NH + N, consequently amounts to 64%. The cross section of the reaction could be fitted by the expression sigma = (2.4 +/- 0.4) x 10(-16) E-1.04 +/- 0.02 cm(2), which leads to a thermal reaction rate of k(T) = (1.0 +/- 0.2) x 10(-7)(T/300)(-0.51 +/- 0.02) cm(3) s(-1), in favorable agreement with previous flowing afterglow Langmuir probe measurements at room temperature, although our temperature dependence is very different. The implications of these measurements for the chemistry of interstellar clouds are discussed. A standard model calculation for a dark cloud predicts a slight increase of N2H+ in the dark clouds but a five- to sevenfold increase of the NH concentration as steady state is reached.
At the heavy ion storage ring CRYRING in Stockholm, Sweden, we have investigated the dissociative recombination of DCOOD{sup +}{sub 2} at low relative kinetic energies, from approx1 meV to 1 eV. The ...thermal rate coefficient has been found to follow the expression k(T) = 8.43 x 10{sup -7} (T/300){sup -0.78} cm{sup 3} s{sup -1} for electron temperatures, T, ranging from approx10 to approx1000 K. The branching fractions of the reaction have been studied at approx2 meV relative kinetic energy. It has been found that approx87% of the reactions involve breaking a bond between heavy atoms. In only 13% of the reactions do the heavy atoms remain in the same product fragment. This puts limits on the gas-phase production of formic acid, observed in both molecular clouds and cometary comae. Using the experimental results in chemical models of the dark cloud, TMC-1, and using the latest release of the UMIST Database for Astrochemistry improves the agreement with observations for the abundance of formic acid. Our results also strengthen the assumption that formic acid is a component of cometary ices.
The dissociative recombination of protonated propionitrile, CH 3 CH 2 CNH + , has been investigated at the heavy ion storage ring, CRYRING, at the Manne Siegbahn Laboratory, Stockholm University, ...Sweden. The thermal rate coefficient has been deduced to follow k ( T ) = (1.5 ± 0.2) × 10 –6 ( T /300) –0.76 ± 0.02 cm 3 s –1 for electron temperatures ranging from ~10 to ~1000 K. Measurements of the branching fractions were performed at ~0 eV relative kinetic energy. It has been found that in 43% ± 2% of the reactions the four heavy atoms remain in the same product fragment. An equal portion of the reactions leads to products where one of the heavy atoms is split off from the other three and 14% ± 1% result in a breakup into two heavy fragments containing two heavy atoms each. We discuss the significance of the data to Titan's upper atmosphere.
Nitrile ions are abundant in Titan's upper atmosphere and are expected to be lost mainly via dissociative recombination with free electrons. We review in this paper a series of experimental results ...on the dissociative recombination reactions of nitrile ions known/expected to be present in Titan's upper atmosphere. The experiments were all performed at the heavy ion storage ring CRYRING in Stockholm, Sweden, and the results presented here include information on rate coefficients at electron temperatures relevant for Titan's upper atmosphere as well as information on the product branching fractions of the reactions. We discuss implications of the results for Titan's atmosphere. As an example the presented results support a statement by Krasnopolsky (2009) that nitriles do not degrade to yield N2 again in Titan's atmosphere, indicating that condensation and polymerization with precipitation to the surface are their ultimate fate.
► CRYRING experiments on the dissociative recombination of nitrile ions are reviewed. ► The studied reactions are relevant for Titan's ionospheric chemistry. ► The provided data are useful in chemical models of Titan's ionosphere. ► Observed preservations of the C-N bonds upon dissociative recombination.
CH3+ is an important molecular ion in the astrochemistry of diffuse clouds, dense clouds, cometary comae, and planetary ionospheres. However, the rate of one of the major destruction mechanisms of ...CH3+, dissociative recombination (DR), has long been uncertain, hindering the use of CH3+ as an astrochemical probe. Here, we present the first absolute measurement of the DR of vibrationally cold CH3+, which has been made using the heavy storage ring CRYRING in Stockholm, Sweden. From our collision-energy-dependent cross sections, we infer a thermal rate constant of k(T) = 6.97(+/- 0.03) x 10(-7)(T/300)(-0.61(+/- 0.01)) cm(3) s(-1) over the region 10 K <= T <= 1000 K. At low collision energies, we have measured the branching fractions of the DR products to be CH3 (0.00(- 0.00)(+ 0.01)), CH2 + H (0.35(-0.01)(+ 0.01)), CH + 2H (0.20(-0.02)(+0.02)), CH + H-2 (0.10(-0.01)(+0.01)), and C + H-2 + H (0.35(-0.02)(+ 0.01)), indicating that two or more C-H bonds are broken in 65% of all collisions. We also present vibrational calculations which indicate that the CH3+ ions in the storage ring were relaxed to the vibrational ground state by spontaneous emission during the storage time. Finally, we discuss the implications of these new measurements for the observation of CH3+ in regions of the diffuse interstellar medium where CH+ is abundant.
Branching ratios and absolute cross sections have been measured for the dissociative recombination of DCCCN+ and DCCCND+ using the CRYRING ion storage ring. In the case of DCCCN+ the dissociation ...yielding D + C3N and those leading to two fragments containing a pair of heavy atoms dominate, whereas pathways producing a fragment with three heavy atoms play only a minor role. Conversely, for DCCCND+, only those channels preserving the carbon chain or producing two fragments with a pair of heavy atoms each are detected. The cross sections of the reactions are very similar and can be fitted to the expressions sigma = (2.9 +/- 0.5) x 10(-15)E(eV)(-1.05 +/- 0.02) cm(2) and sigma = (2.3 +/- 0.4) x 10(-15)E(eV)(-1.10 +/- 0.02) cm(2) for DCCCN+ and DCCCND+, respectively. From these data, thermal reaction rates of k(T) = (1.5 +/- 0.3) x 10(-6)(T/300 K)(-0.60 +/- 0.02) cm(3) s(-1) and k(T) = (1.5 +/- 0.3) x 10(-6)(T/300 K)(-0.58 +/- 0.02) cm(3) s(-1) were calculated for DCCCN+ and DCCCND+, respectively. These rates and branching ratios are compared with those hitherto used in astrophysical models.
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