S. Rosén

Dissociative recombination of D3O+ and H3O+: Absolute cross sections and branching ratios

Dissociative recombination of the polyatomic ions D3O+ and H3O+ with electrons have been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). Absolute cross sections have been determined from 0.001 eV to 0.25 eV center-of-mass energy for D3O+ and from 0.001 eV to 28 eV for H3O+. The cross sections are large (7.3×10−13 cm2 for D3O+ and 3.3×10−12 cm2 for H3O+ at 0.001 eV). At low energies, the cross sections for D3O+ are E−1 energy dependent whereas it is slightly steeper for H3O+. A similar E−1 energy dependence was also observed by Mul et al. [J. Phys. B 16, 3099 (1983)] with a merged electron-ion beam technique for both H3O+ and D3O+ and by Vejby-Christensen et al. [Astrophys. J. 483, 531 (1997)] with the ASTRID storage ring in Denmark, who presented relative cross sections for H3O+. A resonance has been observed around 11 eV for H3O+. It reflects an electron capture to Rydberg states converging to an excited ionic core. A similar structure was reported by Vejb...

Dissociative recombination and excitation of O2+: Cross sections, product yields and implications for studies of ionospheric airglows

We present experimental data on the dissociative recombination (DR) and the dissociative excitation (DE) of O2+ in its electronic and vibrational ground state using a heavy ion storage ring. The absolute DR cross section has been determined over an electron collision energy range from 1 meV to 3 eV. The thermal DR rate coefficient is derived; α(Te)=2.4×10−7(300/Te)0.70±0.01 cm3 s−1, for T>200 K. The threshold for DE was observed near its energetic threshold of 6.7 eV. The DE cross section curve has a maximum of 3×10−16 cm2 near 15 eV. We have determined the branching fractions to the different dissociation limits and present atomic quantum yields for the DR process between 0 to 300 meV collision energy. The quantum yield of O(1D) is found to be 1.17±0.05, largely independent of the electron energy. Arguments are presented that the branching fraction to O(3P)+O(1S) is negligible. The branching fraction to the O(1S)+O(1D) is smaller than 0.06 and varies strongly as a function of collision energy. The O(1S) ...

Dissociative Recombination of HCNH+: Absolute Cross-Sections and Branching Ratios

The dissociative recombination (DR) of HCNH+ has been studied at the heavy ion storage ring CRYRING. The absolute cross-sections have been measured between 0.01 meV and 0.2 eV collision energy. The DR thermal rate coefficients, which can be directly applied to modeling environments in thermal equilibrium, have been found to be 2.8 × 10-7(300/T)0.65 at temperatures T < 1000 K. The DR branching fractions have been measured for different dissociation channels: HCN(HNC)+H (0.67), CN+H2 (0.0), and CN+H+H (0.33) at collision energy of 0 eV. The results show that DR of HCNH+ is an efficient process leading to formation of HCN or HNC isomers, whereas CN production is dominated by three-body fragmentation. The multireference self-consistent calculations in a complete active space have been used as a common background for all studied species and reaction paths. Three-body fragmentation CN+H+H has been considered in one concerted elementary reaction step.

Dissociative Recombination and Excitation of CH5+: Absolute Cross Sections and Branching Fractions

The heavy-ion storage ring CRYRING was used to measure the absolute dissociative recombination and dissociative excitation cross sections for collision energies below 50 eV. Deduced thermal rates coefficients are consistent with previous beams data but are lower by a factor of 3 than the rates measured by means of the flowing afterglow Langmuir probe technique. A resonant structure in dissociative recombination cross section was found at 9 eV. We have determined the branching fractions in DR of CH+5 below 0.2 eV. The branching is dominated by three-body CH3 + H + H and CH2 + H2 + H dissociation channels, which occur with branching ratios of ≈ 0.7 and ≈ 0.2, respectively; thus methane is a minor species among dissociation products. Both the measured absolute cross sections and branching in dissociative recombination of CH+5 can have important implications for the models of dense interstellar clouds and abundance of CH2, CH3 and CH4 in these media.

Branching Fractions in Dissociative Recombination of CH2

The absolute cross section and branching ratios for dissociative recombination of CH -->+2 with electrons have been measured by means of the heavy-ion storage ring CRYRING. Contrary to what has been previously believed, recombination of CH -->+2 is dominated by the three-body channel C + H + H (63%), whereas breakup into the CH + H and C + H2 channels occurs with branching ratios of 25% and 12%, respectively. The thermal rate coefficient for dissociative recombination at 300 K is 6.4 × 10-7 cm3 s-1, which is higher by a factor of 2.5 than the value used in modeling dark molecular clouds. The low CH production and the high production of energetic carbon atoms could be favorable factors for the turbulence model to explain the large abundance of interstellar CH+. The cross section for dissociative excitation was also measured and found to be in good agreement with results from a crossed electron-ion beam experiment.

Branching Fractions in Dissociative Recombination of CH{sup {plus}} {sub 2}

The absolute cross section and branching ratios for dissociative recombination of CH -->+2 with electrons have been measured by means of the heavy-ion storage ring CRYRING. Contrary to what has been previously believed, recombination of CH -->+2 is dominated by the three-body channel C + H + H (63%), whereas breakup into the CH + H and C + H2 channels occurs with branching ratios of 25% and 12%, respectively. The thermal rate coefficient for dissociative recombination at 300 K is 6.4 × 10-7 cm3 s-1, which is higher by a factor of 2.5 than the value used in modeling dark molecular clouds. The low CH production and the high production of energetic carbon atoms could be favorable factors for the turbulence model to explain the large abundance of interstellar CH+. The cross section for dissociative excitation was also measured and found to be in good agreement with results from a crossed electron-ion beam experiment.

Dissociative recombination of NH4+ and ND4+ ions: storage ring experiments and ab initio molecular dynamics.

The dissociative recombination (DR) process of NH4+ and ND4+ molecular ions with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The absolute cross sections for DR of NH4+ and ND4+ in the collision energy range 0.001-1 eV are reported, and thermal rate coefficients for the temperature interval from 10 to 2000 K are calculated from the experimental data. The absolute cross section for NH4+ agrees well with earlier work and is about a factor of 2 larger than the cross section for ND4+. The dissociative recombination of NH4+ is dominated by the product channels NH3+H (0.85+/-0.04) and NH2+2H (0.13+/-0.01), while the DR of ND4+ mainly results in ND3+D (0.94+/-0.03). Ab initio direct dynamics simulations, based on the assumption that the dissociation dynamics is governed by the neutral ground-state potential energy surface, suggest that the primary product formed in the DR process is NH3+H. The ejection of the H atom is direct and leaves the NH3 molecule highly vibrationally excited. A fraction of the excited ammonia molecules may subsequently undergo secondary fragmentation forming NH2+H. It is concluded that the model results are consistent with gross features of the experimental results, including the sensitivity of the branching ratio for the three-body channel NH2+2H to isotopic exchange.

First storage of ion beams in the Double Electrostatic Ion-Ring Experiment: DESIREE

We report on the first storage of ion beams in the Double ElectroStatic Ion Ring ExpEriment, DESIREE, at Stockholm University. We have produced beams of atomic carbon anions and small carbon anion molecules (C(n)(-), n = 1, 2, 3, 4) in a sputter ion source. The ion beams were accelerated to 10 keV kinetic energy and stored in an electrostatic ion storage ring enclosed in a vacuum chamber at 13 K. For 10 keV C2 (-) molecular anions we measure the residual-gas limited beam storage lifetime to be 448 s ± 18 s with two independent detector systems. Using the measured storage lifetimes we estimate that the residual gas pressure is in the 10(-14) mbar range. When high current ion beams are injected, the number of stored particles does not follow a single exponential decay law as would be expected for stored particles lost solely due to electron detachment in collision with the residual-gas. Instead, we observe a faster initial decay rate, which we ascribe to the effect of the space charge of the ion beam on the storage capacity.

Recombination of simple molecular ions studied in storage ring: dissociative recombination of H2O+

Dissociative recombination of vibrationally relaxed H2O+ ions with electrons has been studied in the heavy-ion storage ring CRYRING. Absolute cross-sections have been measured for collision energies between 0 eV and 30 eV. The energy dependence of the cross-section below 0.1 eV is found to be much steeper than the E-1 behaviour associated with the dominance of the direct recombination mechanism. Resonant structures found at 4 eV and 11 eV have been attributed to the electron capture to Rydberg states converging to electronically excited ionic states. Complete branching fractions for all dissociation channels have been measured at a collision energy of 0 eV. The dissociation process is dominated by three-body H + H + O breakup that occurs with a branching ratio of 0.71.

Dissociative recombination of D+(D2O)2 water cluster ions with free electrons

Dissociative recombination (DR) of the water cluster ion D+(D2O)2 has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). Cluster ions were injected into the ring and accelerated to an energy of 2.28 MeV. The stored ion beam was merged with an almost monoenergetic electron beam, and neutral fragments produced by DR were detected by an energy-sensitive surface barrier detector. The first experimental determinations of the absolute DR cross section and branching ratios for a cluster ion are reported. The cross section for the process D+(D2O)2+e− is large and reaches 6⋅10−12 cm2 at a low center-of-mass collision energy of 0.001 eV. The cross section has an E−1.19±0.02 dependence in the energy range 0.001–0.0052 eV, and a steeper slope with an E−1.70±0.12 dependence for E=0.052–0.324 eV. The general trends are similar to the results for previously studied molecular ions, but the cross section is higher in absolute numbers for the cluster ion. Thermal rate coefficients for electron temperatures of 50–2000 K are deduced from the cross section data and the rate coefficients are consequently also large. Branching ratios for the product channels are determined with a grid technique. Break-up into 2D2O+D is the dominating dissociation channel with a probability of 0.94±0.04. The channel resulting in the fragments D2O+OD+D2 has a probability of 0.04±0.02, and the probability for formation of D3O+D2O is 0.02±0.03. The results are compared with data for molecular ions, and the cluster dissociation dynamics are discussed.Dissociative recombination (DR) of the water cluster ion D+(D2O)2 has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). Cluster ions were injected into the ring and accelerated to an energy of 2.28 MeV. The stored ion beam was merged with an almost monoenergetic electron beam, and neutral fragments produced by DR were detected by an energy-sensitive surface barrier detector. The first experimental determinations of the absolute DR cross section and branching ratios for a cluster ion are reported. The cross section for the process D+(D2O)2+e− is large and reaches 6⋅10−12 cm2 at a low center-of-mass collision energy of 0.001 eV. The cross section has an E−1.19±0.02 dependence in the energy range 0.001–0.0052 eV, and a steeper slope with an E−1.70±0.12 dependence for E=0.052–0.324 eV. The general trends are similar to the results for previously studied molecular ions, but the cross section is higher in absolute numbers for the cluster ion. Thermal rate coef...