Abstract
It is demonstrated that a previously developed topological expression for the total π-electron energy of aromatic molecules provides a good qualitative account of localization energies. The logarithm of the ratio of the algebraic structure counts for the ground state and the localized reaction intermediate is the principle energy determining factor. This expression fails for hydrocarbons with unusually small HOMO-LUMO separations. An alternative topological expression that includes a correction for this situation provides an excellent non-empirical explanation for the successful empirical use of Dewar reactivity numbers in correlating exact localization energies. The present analysis provides an explanation for the success of the traditional resonance structure counting technique in predicting relative rates of aromatic substitution. The analysis develop applied only to alternant hydrocarbons.
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