Abstract

1,3-Cyclohexadiene ring opening has been studied within the bonding evolution theory (BET) framework. We have focused on describing for the first time the electron pair rearrangements leading to the cis-1,3,5-hexatriene (HT) product from CHD. The nature of bonding in this process begins with the weakening of the double bonds in the Franck-Condon region. Along the 1(1)B surface, the C-C sigma bond weakens. Meanwhile, its density redistributes toward the whole CHD ring, mainly over double bonds. Breaking of this bond occurs on the 2(1)A surface due to the symmetrical splitting of pair density from this region. This density redistributes toward the reaction center once the pericyclic minimum is reached. The formation of the double bonds that characterize HT occurs gradually in the ground state. However, near the 2(1)A/1(1)A intersection, these bonds are partially established.