The substituent effects on O-H and O-CH 3 bond dissociation energies for a series of 18 parasubstituted phenols (p-XC 6 H 4 OH) and 11 para-substituted anisoles have been studied using the density functional method in order to understand the origin of these effects. The calculated substituent effects agree well with experimental measurements for phenols but are substantially larger than the reported values for anisoles. Both ground-state effect and radical effect contribute significantly to the overall substituent effect. An electron-donating group causes a destabilization in phenols or anisoles (ground-state effect) but a stabilization in the phenoxy radicals (radical effect), resulting in reduced O-R bond dissociation energy. An electron-withdrawing group has the opposite effect. In most cases, the radical effect is more important than the ground-state effect. There is a good correlation between the calculated radical effects and calculated variations in charge and spin density on the phenoxy oxygen. This supports the concept that both polar and spin delocalization effects influence the stability of the phenoxy radical. While almost every parasubstituent causes a stabilization of the phenoxy radical by spin delocalization, electron-donating groups stabilize and electron-withdrawing groups destabilize the phenoxy radical by the polar effect.

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