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Synopsis The decay of hot copper dimer anions is studied in a cryogenic storage ring. We detect atomic anion and neutral products and determine the fragmentation and vibrational autodetachment (VAD) rates separately. For short storage times the dimer anions predominantly decay by fragmentation of highly rotationally excited ions by tunneling through the rotational barrier. For storage times exceeding 100 ms, however, VAD is dominating. This process is driven by the very weak direct coupling between nuclear and electronic degrees of freedom.

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 ...

The dissociative recombination of protonated propionitrile, CH3CH2CNH+, has been investigated at the heavy ion storage ring, CRYRING, at the Manne Siegbahn Laboratory, Stockholm University, Sweden. ...

At the heavy ion storage ring CRYRING in Stockholm, Sweden, we have investigated the dissociative recombination of DCOOD2+ at low relative kinetic energies, from ~1 meV to 1 eV. The thermal rate coefficient has been found to follow the expression k(T) = 8.43 × 10-7 (T/300)^-0.78 cm3 s-1 for electron temperatures, T, ranging from ~10 to ~1000 K. The branching fractions of the reaction have been studied at ~2 meV relative kinetic energy. It has been found that ~87% 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.

Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH2CHCNH+, have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at~2meV relative kinetic energy about 50% of the DR events involve only ruptures of X–H bonds (where X=C or N)while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H2). The absolute DR cross section has been investigated for relative kinetic energies ranging from ~1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 × 10-6 (T/300)-0.80 cm3 s-1 for electron temperatures ranging from ~10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan’s upper atmosphere are discussed.

Branching ratios and absolute cross sections have been measured for the dissociative recombination of HCS+ and OCS+ at the CRYRING ion storage ring. In the case of OCS+, the channel leading to CO + S (83%) dominates, whereas the other exoergic pathways leading to CS + O (14%) and C + SO (3%) are of lesser importance. In the case of HCS+, fracture of the C–S bond is predominant (81%), with the production of H + CS accounting for the remainder (19%). The cross section of the reaction could be fitted by the expressions σ = 1.41 × 10-15E(eV)-1.11 and 4.47 × 10-16E(eV)-1.14 cm2 for HCS+ and OCS+, respectively. The derived energy dependences of the thermal reaction rate coefficients can be fitted by k(T) = 9.7 × 10-7(T/300)-0.57 and 3.5 × 10-7(T/300)-0.62 cm3 s-1 for HCS+ and OCS+, respectively. We use these data to perform model calculations on the HCS+/CS abundance ratio in dark clouds and find that the models using the UMIST and Ohio State University databases have even more difficulty in accounting for the large observed ratio.

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 y ...

The dissociative recombination of fully deuterated protonated acetonitrile, CD(3)CND(+), has been investigated at the CRYRING heavy ion storage ring, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Branching fractions were measured at approximately 0 eV relative collision energy between the ions and the electrons and in 65% of the DR events there was no rupture of bonds between heavy atoms. In the remaining 35%, one of the bonds between the heavy atoms was broken. The DR cross-section was measured between approximately 0 eV and 1 eV relative collision energy. In the energy region between 1 meV and 0.1 eV the cross section data were best fitted by the expression sigma = 7.37 x 10(-16) (E/eV)(-1.23) cm(2), whereas sigma = 4.12 x 10(-16) (E/eV)(-1.46) cm(2) was the best fit for the energy region between 0.1 and 1.0 eV. From the cross section a thermal rate coefficient of alpha(T) = 8.13 x 10(-7) (T/300)(-0.69) cm(3) s(-1) was deduced.

Dissociative recombination of the deuterated acetaldehyde ion CD3CDO(+) has been studied at the heavy-ion storage ring CRYRING, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Product branching fractions together with absolute DR cross-sections were measured. The branching fractions were determined at a relative collision energy between the ions and the electrons of approximately 0 eV. With a probability of 34% the DR events resulted in no ruptures of bonds between heavy atoms (i.e. no breakage of the C-C bond or the C[double bond, length as m-dash]O bond). In the remaining 66% of the events one of the bonds between the heavy atoms was broken. The energy-dependent cross-section for the DR reaction was measured between approximately 0 and 1 eV relative kinetic energy. In the energy region between 1 meV and 0.2 eV the absolute cross section could be fitted by the expression sigma(E) = 6.8 x 10(-16)E(-1.28) cm(2), whereas in the energy interval between 0.2 and 1 eV the data were best fitted by sigma(E) = 4.1 x 10(-16)E(-1.60) cm(2). From these cross section data the thermal rate coefficient (as a function of the electron temperature), alpha(T) = 9.2 x 10(-7) (T/300)(-0.72) cm(3) s(-1) was obtained.

Dimethyl disulfide (DMDS) and N-methylacetamide are two first choice model systems that represent the disulfide bridge bonding and the peptide bonding in proteins. These molecules are therefore suitable for investigation of the mechanisms involved when proteins fragment under electron capture dissociation (ECD). The dissociative recombination cross sections for both protonated DMDS and protonated N-methylacetamide were determined at electron energies ranging from 0.001 to 0.3 eV. Also, the branching ratios at 0 eV center-of-mass collision energy were determined. The present results give support for the indirect mechanism of ECD, where free hydrogen atoms produced in the initial fragmentation step induce further decomposition. We suggest that both indirect and direct dissociations play a role in ECD.

Aims: Determination of branching fractions, cross sections and thermal rate coefficients for the dissociative recombination of CD3OCD2+ (0-0.3 eV) and (CD3)2OD+ (0-0.2 eV) at the low relative kinet ...

The dissociative recombination of the acetaldehyde cation, CH(3)CHO(+), has been investigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. The dependence of the absolute cross section of the reaction on the relative kinetic energy has been determined and a thermal rate coefficient of k(T) = (1.5 ± 0.2) × 10(-6) (T/300)(-0.70±0.02) cm(3) s(-1) has been deduced, which is valid for electron temperatures between ∼10 and 1000 K. The branching fractions of the reaction were studied at ∼0 eV relative kinetic energy and we found that breaking one of the bonds between two of the heavy atoms occurs in 72 ± 2% of the reactions. In the remaining events the three heavy atoms stay in the same product fragment. While the branching fractions are fairly similar to the results from an earlier investigation into the dissociative recombination of the fully deuterated acetaldehyde cation, CD(3)CDO(+), the thermal rate coefficient is somewhat larger for CH(3)CHO(+). Astrochemical implications of the results are discussed.

The vibrational population of the hydroxyl radical, OH, formed in the OH+H+H channel arising from the dissociative recombination of the hydronium ion, H(3)O(+), has been investigated at the storage ring CRYRING using a position-sensitive imaging detector. Analysis shows that the OH fragments are predominantly produced in the v=0 and v=1 states with almost equal probabilities. This observation is in disagreement with earlier FALP experiments, which reported OH(v=0) as the dominant product. Possible explanations for this difference are discussed.

Alcohols and nitriles not only play an important role as templates for synthesis of larger molecules in the interstellar medium and planetary atmospheres, but they can also be regarded as precursors for biomolecules. Alcohols can form carbohydrates through reaction with HCO and nitriles can be hydrolysed to amino acids in aqueous solutions, which is the final step of the well-known Strecker synthesis. Therefore the question of the pathways of formation of alcohols and nitriles and the efficiency and the product distribution of their subsequent degradation reactions in the above-mentioned astrophysical environments is of great interest. In both processes dissociative recombination reactions of protonated nitriles and alcohols may play a major role and are included in models of interstellar clouds and planetary atmospheres. However, the reaction rate coefficients and product branching ratios for the majority of these processes are so far still unknown, which adversely affects the quality of predictions of model calculations. In this Contribution, we therefore present branching ratios and rate constants of the dissociative recombination of protonated methanol (CH3OH2), as well as protonated acetonitrile (CH3CNH+), acrylonitrile (C2H3CNH+) and cyanoacetylene (HC3NH+). The impact of the obtained new data on model calculations of abundances of important interstellar molecules in dark clouds is discussed.

The branching ratios of the different reaction pathways and the overall rate of the dissociative recombination of CD3OD + were measured at the CRYRING storage ring located at the Manne Siegbahn Laboratory in Stockholm, Sweden. A preliminary analysis of the data yielded that formation of methanol accounts for only 6 ± 2 % of the total reaction rate. Largely, dissociative recombination of CD3OD + involves fragmentation of the C-O bond, the major process being the three-body break-up forming CD3, OD and D (branching ratio 0.59). A non- negligible formation of interstellar methanol by the previously proposed mechanism is therefore very unlikely.