Polyacene and cyclacene geometries and electronic structures: Bond equalization, vanishing band gaps, and triplet ground states contrast with polyacetylene

The ground-state geometries and excited singlet and lowest triplet energies of polyacenes from benzene through nonacene are predicted with B3LYP/6-31G * calculations and compared to experimental data where available. The resul ts are compared to these data for cyclacenes and polyenes. The polyacenes a nd cyclacenes have geometries consisting of two fully delocalized nonaltern ating ribbons joined by relatively long bonds. Polyacenes are predicted to have smaller band gaps than the corresponding polyenes and triplet ground s tates for nine or more benzene rings. The fully delocalized nonalternating nature of polyacenes differs from the bond alternation resulting from Peier ls distortion in polyenes. The differences are rationalized in terms of a s imple MO model, and the results are compared to extensive prior theoretical work in the literature. Predictions about the electronic structure of anal ogues containing polyacene units are made.