Abstract
The mechanisms of some positive and negative ion—molecule reactions have been determined by a quantitative ion cyclotron double-resonance technique with isotopically labelled reactants. Four types of mechanism were elucidated: charge transfer, ion transfer, atom abstraction and complex formation. Thus, charge transfer is shown to be the only major reaction channel in the systems CO + + CO 2, SO − + SO 2, and O − + NO 2, while in the system Cl 2 − + Cl 2 CO ion transfer is the main mechanism, and complex formation with oxygen-atom scrambling is the major channel in O − + N 2O. The experimental results also point out cases where the reaction proceeds by more than one mechanism as, for example, in the reaction system H 2O + + H 2O.
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