How delocalized are the polyacenes?

Abstract

AbstractIn an attempt to quantify electron delocalization in polyacenes with up to 50 carbon atoms, we have performed self‐consistent field calculations in which the 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 framework. We find that the energetic cost of localizing the 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 electrons.