Chemical Bond Energies\nof Organic Peroxides: From\nCH<sub>3</sub>OOCH<sub>3</sub> to High-Molecular-Weight Industrially\nSignificant Compounds

Peroxides are of some importance in a number of industrial\nareas,\nas well as in atmospheric and low-temperature combustion chemistries.\nAlthough there are some organic peroxides that are powerful explosives,\nsuch as hexamethylene triperoxide diamine, their principal use is\nas initiators in polymerization reactions in the plastics and rubber\nindustries since the O–O bond is easily cleaved to generate\ntwo reactive free radicals. This gives rise to concern about safety\nissues in both the manufacture of and the deployment of these compounds\nsince they are strong oxidizers. A measure of these safety concerns\ncan be achieved by determining the chemical bond energy or bond dissociation\nenergy (BDE) for the following process: R–O–O–R′\n→ RO<sup>•</sup> + R′O<sup>•</sup> since\nthose with very weak O–O bonds are most likely to be problematic.\nWe have used the midlevel model chemistry G4 to compute the BDE of\na number of organic peroxides ranging from the simplest dialkyl peroxide\nto diacyl, peroxy ester, and peroxycarbonate peroxides. In addition,\nwe have used much higher levels of theory to benchmark the chemical\nbond energy of dimethyl peroxide in the expectation that this will\nanchor all future determinations.