title: Fundamental Aspects of Recoupled Pair Bonds. III. The Frustrated Recoupled Pair Bond in Oxygen Monofluoride.
abstract: In a previous paper in this series, we discussed the formation of recoupled pair bonds in the a4Σ-states of CF and SF in which the recoupling process was essentially complete at the equilibrium geometry of the molecule. In this paper, we examine thea4Σ-state of oxygen monofluoride (OF), which could also have a recoupled pair bond. Unlike the other two molecules, generalized valence bond calculations predict that the recoupling in OF is woefully incomplete at Reand the resulting potential energy curve for the OF(a4Σ-) state is purely repulsive; the binding energy, ≈11 kcal/mol, is entirely due to dynamical correlation. A number of factors account for these differences, but the nature of the dominant correlation effect in the oxygen 2p lone pair as well as the spatial extent of the 2p orbital are paramount.
authors.affiliation: Department of Chemistry, University of California, Berkeley , Berkeley, California 94720, United States.
authors.forename: Tyler Y
authors.initials: TY
authors.lastname: Takeshita
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign , 600 S. Mathews Avenue, Urbana, Illinois 61801, United States.
authors.forename: Thom H
authors.initials: TH
authors.lastname: Dunning