Reduced HOMO−LUMO Gap as an Index of Kinetic Stability for Polycyclic Aromatic Hydrocarbons

Abstract

A reduced HOMO−LUMO gap, which is defined as the HOMO−LUMO energy separation of a molecule divided by that of the hypothetical polyene reference, can be used as an index of kinetic stability for a variety of polycyclic aromatic hydrocarbons (PAHs). The reduced HOMO−LUMO gap < 1.00 indicates that the HOMO contributes to the decrease in the topological resonance energy. In general, PAHs with reduced HOMO−LUMO gaps < 1.30 are chemically very reactive. Fully benzenoid hydrocarbons are kinetically very stable with very large reduced HOMO−LUMO gaps. Many of the PAH molecules with large reduced HOMO−LUMO gaps are closed-shell substructures of nonmetallic one-dimensional benzenoid polymers.