Aromaticity: an ab Initio Evaluation of the Properly Cyclic Delocalization Energy and the π-Delocalization Energy Distortivity of Benzene

Abstract

A complete active space self-consistent field (CASSCF) calculation of the pi system of a conjugated molecule enables one to define optimal valence pi and pi* molecular orbitals (MOs). One may define from them a set of atom-centered orthogonal pi orbitals, one per carbon atom, and the resulting upper multiplet is used to define the pi-electron delocalization energy. This quantity is confirmed to be slightly distortive, i.e., to prefer bond-alternated geometries. One may also define strongly localized bond MOs corresponding to a Kekule structure and then perturb the associated strongly localized single determinant under the effect of the delocalization between the bonds and of the electronic correlation. The third order of perturbation introduces the contribution of the cyclic circulation of the electrons around the benzene ring, i.e. the aromatic energy contribution. Its value is about 1.5 eV. It is antidistortive, but remains important under bond alternation. The cyclic correlation effects are of minor importance.