The nonpolar resonance effects and the non-Hammett behaviors

In the study we tried to unify the observed non-Hammett behaviors in various fields by proposing the nonpolar resonance effect. This effect was shown to be important not only for carbon radicals but also for some closed-shell systems. Therefore, the odd electron or spin is not the essential cause of the effect. The real origin of the non-Hammett effect should be the HOMO(reaction-center)-LUMO(acceptor) and LUMO(reaction-center)-HOMO(donor) interactions. This means that the nonpolar resonance effect is a universal effect. However, we found that the nonpolar resonance effect could not be well exhibited in many systems because of the serious competition from the polar Hammett effect. Finally, we showed that our proposal of the nonpolar resonance effect was valuable from a practical point of view, because using it we could perform much better correlation studies on some "tough" problems such as radical and multiple bond stabilities, UV and IR spectra, and molecular structures.