How delocalized are the polyacenes?

In an attempt to quantify electron delocalization in polyacenes with up to 50 carbon atoms, we have performed self-consistent field calculations in which the π $$ \pi $$ electrons are constrained to occupy highly localized molecular orbitals (HILOs) centered on a maximum of two, six or ten adjacent carbon atoms. We have also performed similar calculations on simple polyacene analogs consisting only of hydrogen atoms and exhibiting electron delocalization in the σ $$ \sigma $$ framework. We find that the energetic cost of localizing the π $$ \pi $$ electrons in the polyacenes is roughly 60, 5 or 0.1 kJ/mol per ring atom for the two-, six- and ten-atom HILOs, respectively, and the use of these localized models overestimates the predicted hydrogenation energies of the acenes by roughly 50%, 4% and 0.1%, respectively. We conclude that the chemistry of polyacenes can be modeled well using highly localized descriptions of the π $$ \pi $$ electrons.