The role of delocalization in benzene

The influence of [pi] delocalization on the geometry of benzene is examined at the ab initio SCF level of theory. We find that benzene favors a bond alternating geometry when its canonical [pi] MOs are replaced by three localized ethylenic orbitals, revealing that delocalization is in part responsible for the equilibrium symmetric structure. In apparent contrast, a [sigma]-[pi] energy partitioning analysis suggests that the benzene [sigma] framework is responsible for the symmetric structure, the [pi] system preferring a distorted geometry. Shaik et al. have therefore concluded that delocalization in not an important symmetrizing force in this molecule. We show, however, that the [pi] energy component contains a sizable and strongly geometry dependent contribution from the localized (Kekule) wave function. Thus, it appears to be misleading to judge the nature of delocalization based on a [sigma]-[pi] partition. We conclude that delocalization effects act to strongly stabilize symmetric benzene in essential accord with the concepts of classical resonance theory. 27 refs., 6 figs., 2 tabs.