[4+4] reactions are forbidden in the ground state and often entropically disfavored in the excited state. The mechanism of the [4+4] photocycloaddition is proposed to begin with the photoexcitation of a 1,3-diene system into the excited state. Because the orbital symmetry of the highest occupied molecular orbital (HOMO) in the excited diene is the same as that of the lowest unoccupied molecular orbital (LUMO) in another ground state diene, they are able to form an exciplex that decays to form the closed cyclooctane ring structure. Below is a Frontier Molecular Orbital diagram depicting the interaction between the two molecules of dienes.