Bonding and Electronic Structure of XeF_3~-

摘要

The xenon-fluoride bond dissociation energy in XeF_3~- has been measured by using energy-resolved collision-induced dissociation studies of the ion. The measured value, 0.84 ± 0.06 eV, is higher than that predicted by electrostatic and three-center, four-electron bonding models. The bonding in XeF_3~-is qualitatively described by using molecular orbital approaches, using either a diradical approach or orbital interaction models. Two low-energy singlet structures are identified for XeF_3~-, consisting of Y- and T-shaped geometries, and there is a higher energy D_(3h) triplet state. Electronic structure calculations predict the Y geometry to be the lowest energy structure, which can rearrange by pseudorotation through the T geometry. Orbital correlation diagrams indicate that that ion dissociates by first rearranging to the T structure before losing fluoride.