title: Bonding and electronic structure of XeF3-.
abstract: The xenon-fluoride bond dissociation energy in XeF3- 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 XeF3- 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 XeF3-, consisting of Y- and T-shaped geometries, and there is a higher energy D3h 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.
authors.affiliation: Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, USA.
authors.forename: Ian H
authors.initials: IH
authors.lastname: Krouse
authors.forename: Changtong
authors.initials: C
authors.lastname: Hao
authors.forename: Catherine E
authors.initials: CE
authors.lastname: Check
authors.forename: Kim C
authors.initials: KC
authors.lastname: Lobring
authors.forename: Lee S
authors.initials: LS
authors.lastname: Sunderlin
authors.forename: Paul G
authors.initials: PG
authors.lastname: Wenthold