Differential cross sections, measured with guided ion beams: applications to N+ + N2 and C2H2+ + C2D4 collisions Original Research Article

In gas phase ion chemistry, the guided-ion-beam (GIB) technique is well established for measuring reliable absolute integral cross sections over a wide range of collision energies. It is less known that the method is also well suited for recoil velocity distributions of product ions (the axial component is determined by using the time-off-flight method (GIB-TOF), the transverse component by guiding field variation (GIB-VAR)). This additional information can be used as a diagnostic tool and helps to unravel the energetics of competing reaction pathways. In general, it allows determination of absolute doubly differential cross sections with very high sensitivity and in an energy and scattering angular range inaccessible to standard ion-beam methods. The experimental part of this paper describes the technique in detail, its difficulties and advantages and the required experimental test procedures. Numerical simulations aid the understanding of the kinematics and the shortfalls of the technique, mainly caused by the random motion of the gas in the scattering cell. The results section briefly summarizes already published product velocity distributions obtained for simple systems. New measurements will be presented for two collision systems, N+ + N2 and C2H2+C2D4. For the first one, product velocity distributions provide information on the role of excited states of both reactants and products. In combination with new ab initio calculations of the N3+ potential surface [F.R. Bennett et al., Chem. Phys., this issue] the role of barriers and nonadiabatic interactions is elucidated. In the case of the more complicated hydrocarbon system, the method allows us to distinguish between products of same mass but different isotopic compositions. In addition, different reaction pathways are identified and hints to barrier heights are extracted from the product velocity distributions.