Abstract
The process of H/D isotope exchange within gas-phase cluster ions has been examined for a variety of small proton-bound cluster ions. Product ion distributions from low-energy collision-induced dissociation (CID) of partially deuterated water cluster ions reveal enrichment of deuterium in the neutral water products due to an equilibrium isotope effect wherein deuterium atoms preferentially occupy peripheral sites in the cluster. By comparison, product ion distributions from CID of partially deuterated ammonia cluster ions are controlled by both equilibrium and kinetic isotope effects, compounded by incomplete exchange within the clusters. Isotope exchange reactions and labeling studies have provided information about structures of cluster ions and mechanisms of bimolecular ion-molecule reactions. A summary of these studies is presented.
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