A. Paal

Dissociative Recombination of N2H+: Evidence for Fracture of the N-N Bond

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- → N2 + 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 σ = (2.4 ± 0.4) × 10-16E-1.04±0.02 cm2, which leads to a thermal reaction rate of k(T) = (1.0 ± 0.2) × 10-7(T/300)-0.51±0.02 cm3 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.

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.

CRYRING — a synchrotron, cooler and storage ring

Abstract CRYRING is a small synchrotron and storage ring equipped with electron cooling. Highly charged ions from the electron beam ion source CRYSIS or singly charged ions from the plasmatron source MINIS are injected via an RFQ into the ring. The facility is in the commissioning phase. Full design energy has been achieved and electron cooling demonstrated both for atomic and molecular ions. The experimental program started in August with two projects, dissociative recombination of H+3 ions and radiative recombination to deuterons. The status as of September 20, 1992, is reported.

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.

Studies of electron cooling with a highly expanded electron beam

Abstract The electron cooler at CRYRING is now operating with a superconducting gun solenoid and an electron beam that is adiabatically expanded with a factor of up to 100. This paper describes the new gun solenoid and electron gun. It presents measurements made on longitudinal cooling forces with different expansion factors, electron densities, magnetic field strengths and beam alignments. It also presents studies of a transverse beam instability that appears when a misalignment is introduced between ion and electron beams. Finally, some measurements of dielectronic recombination that directly yield transverse and longitudinal electron temperatures are discussed.

Experimental determination of dissociative recombination of CH2OH+, CD2OD+, and CD2+

Measurements of the cross-sections and branching ratios of the dissociative recombination of the ions CH2OH þ, CD2OD þ and CD2OD þ 2 have been performed at the CRYRING storage ring located in Stockholm, Sweden. Evaluation of the data yielded reaction rate coefficients of: 7.0 10 (T/300) 0.78 cmmol 1 s 1 for CH2OH; 7.5 10 (T/300) 0.70 cmmol 1 s 1 for CD2OD þ and 1.51 10 (T/300) 0.66 cmmol 1 s 1 for CD2OD2 . Calculation of the branching ratios for CH2OH þ and its deuterated isotopologue gave the following results for the DR reaction channels involving C–O bond fissure: H2OþCH (2.2%) and CH2þOH (5.5%) in the reaction of CH2OH þ as well as D2OþCD (5%) and CD2þOD (18%) for the dissociative recombination of CD2OD þ. The remainder of the reaction flux kept the C–O bond intact: 92% for CH2OH þ and 77% for CD2OD þ, respectively. Other recent measurements on the CH3OH þ 2 ion indicate dominating bond breaking between the heavy atoms, which is in contrast to this experiment. For CD2OD þ 2 CO-bond breaking was observed for 43% of the reaction flux.Measurements of the cross-sections and branching ratios of the dissociative recombination of the ions CH2OH+, CD2OD+ and CD2OD2+ have been performed at the CRYRING storage ring located in Stockholm, Sweden. Evaluation of the data yielded reaction rate coefficients of: 7.0 x 10-7( T/300) -0.78 cm3mol-1s -1 for CH2OH+; 7.5 x 10-7(T/300) -0.70 cm3 mol-1s-1 for CD2OD+ and 1.51 x 10-6(T/300)-0.66 cm3 mol-1s-1 for CD2OD2+. Calculation of the branching ratios for CH2OH+ and its deuterated isotopologue gave the following results for the DR reaction channels involving C-O bond fissure: H2O+CH (2.2%) and CH2+OH (5.5%) in the reaction of CH2OH+ as well as D2O+CD (5%) and CD2+OD (18%) for the dissociative recombination of CD2OD+. The remainder of the reaction flux kept the C-O bond intact: 92% for CH2OH+ and 77% for CD2OD+, respectively. Other recent measurements on the CH3OH2+ ion indicate dominating bond breaking between the heavy atoms which is conversely to this experiment. For CD2OD2+ CO-bond breaking was observed for 57% of the reaction flux.

Experimental studies of the dissociative recombination processes for the dimethyl ether ions CD3OCD2+ and (CD3)2OD+

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 ...

Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide

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.

DESIREE as a new tool for interstellar ion chemistry

A novel cryogenic electrostatic storage device consisting of two ion-beam storage rings with a common straight section for studies of interactions between oppositely charged ions at low and well-de ...

Branching ratios and absolute cross sections of dissociative recombination processes of N2O

We have investigated the dissociative recombination of the N2O+ ion using the CRYRING heavy-ion storage ring at the Manne Siegbahn laboratory in Stockholm, Sweden. The dissociative recombination branching ratios were determined at minimal (approximately 0 eV) collision energy, showing that the dominating pathways involved two-body fragmentation: N2 + O (48%) and NO + N (36%). The branching ratio of the three-body break-up 2N + O was 16%. The overall thermal rate coefficient of the title reaction follows the expression k(T) = 3.34 +/- 0.75 x 10(-7) (T/300) (-0.57+/- 0.03 cm3 s(-1)), which correlates perfectly with earlier flowing afterglow studies on the same process.