Bonding and electronic structure of XeF3-.
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.
Krouse
Ian H
IH
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115, USA.
Hao
Changtong
C
Check
Catherine E
CE
Lobring
Kim C
KC
Sunderlin
Lee S
LS
Wenthold
Paul G
PG