Localized Bond Orbital Analysis of the Bonds of O2.

A localized bond orbital analysis of the bonding in dioxygen and related species provides a unique fundamental insight into its bonding characteristics. It reveals the coalescence of the molecular orbital and valence bond/Lewis approaches and clearly demonstrates that the often stated inability of valence bond theory to describe the bonding of O2 is a myth. The analysis indicates that the σ-bond strength of 3O2 is not weak as previously believed and accounts for much of its enhanced stability compared with hydroperoxyl. We attribute the stability and persistence of 3O2 to a combination of this attribute and favorable maximization of exchange coupling between the valence electrons.