Coincidence studies of the bond-forming reactivity and reaction dynamics of molecular dications

This review article discusses the recent progress in explaining and understanding the gas-phase bimolecular reactions of small molecular dications. The article focuses on dication reactions which involve the formation of new chemical bonds and their study by a new position-sensitive coincidence methodology. A review of previous investigations of the bimolecular chemistry of molecular dications is also presented, followed by a detailed description of the position-sensitive coincidence methodology as applied to bimolecular interactions. The insight gained from these position-sensitive experiments is illustrated by a discussion of the results of studies of the reaction of CF22+ with H2O and the reactions of N-2(2+) with a variety of neutral species. The overall conclusion from these investigations is that the bond-forming reactions of molecular dications frequently proceed via the formation of a collision complex. These transitory intermediates may decay to the observed products by either charge-separation or neutral loss. (C) 2006 Elsevier B.V. All rights reserved.