In order to explore structural specialty on reactivity of peroxides

the oxygen-oxygen bond dissociation energy

the oxygen net charges and the calibration charges of free radicals have been caculated via molecular mechanics and AM1 method for decades of organic peroxides.Multiple linear regression was performed for the calculated data with 10h-HLT

which is a kinetic parameter in literature.Results show that the oxygen-oxygen bond dissociation energies of the examined peroxides are not correlated with their 10h-HLT parameters.Since the thermal homolytical cleavage of the peroxide is a reversal process

is includes the decomposition of the parent peroxide and the recombination of the oxygen-centered free radicals.The interaction of the free radicals in the recombination was considered significant.Obtained results indicate that the electronic structure and the spatial topology of radicals mostly influence reactivity of the peroxides.The more the absolute of oxygen charge densities in the free radicals

the easier the dissociation of the parent peroxide.Is was found that the oxygen net charge and the calibration charge of radicals play the key roles in characterization of the reactivity of the peroxides.In the same solvent the four factor linear regression is mostly obeyed between the 10h-HLTs of the parent peroxides and the two oxygen net charges and the two calibration charges for two free radicals.The 10h-HLT valus have thus been predicted by using a correlation with the four factors.