Abstract
The molecular motions of benzoyloxyl radicals in crystals of diacyi peroxides are analyzed by packing energy calculations and by the packing density method. The results are discussed against available experimental evidence on the photolysis of these crystals. It is found that the experimentally observed motions have low energy barriers, and that easy rotation from the standpoint of packing energy corresponds to motion towards empty space. The rotation is calculated to be impossible for a dichloro derivative, so that it is predicted that this compound should react by a different pathway in the solid state.
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