1,3,5-Cyclohexatriene captured in computro; the importance of resonance

Abstract

The geometry and energy of 1,3,5-cyclohexatriene, the reference molecule for the determination of the extra stabilization of benzene, have been calculated using an Ab Initio Valence Bond method. The theoretical resonance energy, according to Dewar, calculated as the energy difference between two-structure benzene and single-structure 1,3,5-cyclohexatriene, both with completely optimized geometries and orbitals, is only −12.05 kcal/mol. Resonance energies of −25.37 (local orbitals), −19.82 (delocal orbitals) and −44.13 (breathing orbitals) kcal/mol are found using the Pauling definition. The concept of the vertical resonance energy, however, is proven to be not tenable beyond a minimal basis.