Richard Thomas

Mutual neutralization of hydronium (H 3 O + ) and hydroxide (OH − ) ions is a very fundamental chemical reaction. Yet, there is only limited experimental evidence about the underlying reaction mechanisms. Here, we report three-dimensional imaging of coincident neutral products of mutual-neutralization reactions at low collision energies of cold and isolated ions in the cryogenic double electrostatic ion-beam storage ring (DESIREE). We identified predominant H 2 O + OH + H and 2OH + H 2 product channels and attributed them to an electron-transfer mechanism, whereas a minor contribution of H 2 O + H 2 O with high internal excitation was attributed to proton transfer. The reported mechanism-resolved internal product excitation, as well as collision-energy and initial ion-temperature dependence, provide a benchmark for modeling charge-transfer mechanisms.

In this paper, we present an apparatus for studies into the photodetachment process of atomic negative ions. State-selective detection of the residual atom following the initial photodetachment step is achieved by combining resonant laser excitation of the photo-detached atom with electric field ionization. The resonance ionization technique in combination with a co-linear ion–laser beam geometry gives an experimental apparatus that has both high selectivity and sensitivity. In addition to measurements of a single selected partial photodetachment channel, the apparatus also can be used to study a manifold of photodetachment channels in which the residual atom is left in a high-lying Rydberg state and for investigation of the double electron-detachment process. Ion-optical simulations in SIMION are used to illustrate the operation of the apparatus for studying such processes. Successful performance of the apparatus against the simulation is demonstrated by a high resolution study of the photodetachment of cesium, where the sharp s-wave threshold of the photodetachment processes leaving the residual atom in the excited 6p state was investigated.