Dissociative recombination of H+(H2O)3 and D+(D2O)3 water cluster ions with electrons: cross sections and branching ratios.

Dissociative recombination (DR) of the water cluster ions H(+)(H(2)O)(3) and D(+)(D(2)O)(3) with electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, absolute DR cross sections have been measured for H(+)(H(2)O)(3) in the energy range of 0.001-0.8 eV, and relative cross sections have been measured for D(+)(D(2)O)(3) in the energy range of 0.001-1.0 eV. The DR cross sections for H(+)(H(2)O)(3) are larger than previously observed for H(+)(H(2)O)(n) (n=1,2), which is in agreement with the previously observed trend indicating that the DR rate coefficient increases with size of the water cluster ion. Branching ratios have been determined for the dominating product channels. Dissociative recombination of H(+)(H(2)O)(3) mainly results in the formation of 3H(2)O+H (probability of 0.95+/-0.05) and with a possible minor channel resulting in 2H(2)O+OH+H(2) (0.05+/-0.05). The dominating channels for DR of D(+)(D(2)O)(3) are 3D(2)O+D (0.88+/-0.03) and 2D(2)O+OD+D(2) (0.09+/-0.02). The branching ratios are comparable to earlier DR results for H(+)(H(2)O)(2) and D(+)(D(2)O)(2), which gave 2X(2)O+X (X=H,D) with a probability of over 0.9.

Importance of an M2 depopulating channel for a Kr II metastable state.

An experimental investigation of the radiative lifetime of the metastable 4s24p4(3P)4d4D7/2 level in Kr II shows an unusual situation regarding the importance of an M2 depopulation channel. While the first order M1 and E2 channels are expected to contribute in a dominant way to the decay, the experimental result, obtained using a laser probing technique on a stored ion beam, tau = 0.57+/-0.03 s, is far too short to be due to these channels according to our relativistic multiconfiguration Dirac-Fock calculation. Only if second order contributions to the decay branches (including essentially the M2 contribution) are taken into account in the calculations could the unexpected short lifetime be explained.

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.

Lifetime measurements of metastable states in Fe+.

The lifetime of two metastable levels in Fe+ has been measured by laser probing of a stored ion beam. In the dense spectrum of Fe+, the metastable levels a (6)S(5/2) and b (4)D(7/2) were selected and their lifetimes were determined to be 230 +/- 30 and 530 +/- 30 ms, respectively. The lifetimes are compared with previous theoretical results. Metastable lifetime measurements of Fe+ are of great importance for interpretation of spectra from astronomical objects. The present experiment opens for the possibilities to investigate lifetimes of metastable states in complex atomic ions, which have, so far, been unexplored.

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.

Dynamics of three-body breakup in dissociative recombination: H(2)O(+).

To better understand the propensity for the three-body breakup in dissociative recombination (DR) of dihydrides ( H(3)(+), NH(2)(+), CH(2)(+), and H(2)O(+)), we undertook a study of the dynamics of this process. A study of DR of H(2)O(+) to give O + H + H was carried out at the CRYRING Heavy-Ion Storage Ring in Stockholm. With the stored beam energy of 4.5 MeV, we separated the O signal from the H signals with a differential absorber, thus reducing the problem to a sum of two two-body problems. Results included (1) the ratio of O((3)P) to O((1)D) product, (2) the distribution of recoil-kinetic energy between the two hydrogen atoms, (3) the angular distribution between the hydrogen atoms in the O((3)P) channel and in the O((1)D) channel.