Mobius strip versus Linear and cyclic polyacenes: a Huckel and semiempirical investigation

The electronic structure of finite and infinite linear, cyclic and Mobius s trip polyacenes has been investigated by adopting Huckel and semiempirical schemes. Using the Huckel approach, it turns out that the Mobius belting pr ocess modifies the highest occupied molecular orbital (HOMO)-lowest unoccup ied molecular orbital(LUMO) gap in such a way its evolution with chain leng th is similar to the linear polyacenes rather than their cyclic analogs. Th ese results are corroborated at the Austin model 1 (AM1) level, where the g eometry relaxation effects are taken into account. The optimized AM 1 struc tures show that the Mobius defect is localized and extends over a third of the ring. With respect to the Huckel approach, accounting for geometry dist ortion at the AM1 levels results in an increase in the HOMO-LUMO gap of the Mobius strip relative to the linear and cyclic finite-size structures. On the other hand. when including electron-hole correlation at the configurati on interaction singles/Zerner's intermediate neglect of differential overla p level the behavior with system size of the first excitation energy of cyc lic and Mobius polyacenes differs from their linear analogs and leads to sm aller singlet excitation energies.