Complications in photochemistry of organic peroxides

In spite of much active work in the photochemistry of organic peroxides particularly as photoinitiators, mechanisms for several processes are still unclear. This article discusses the following mechanistic complications in this area. These include a mechanism leading to the cleavage of the peroxide bond in the excited peroxide molecules, singlet sensitization leading to homolytic cleavage of the peroxide bond in spite of negative free energy change estimated for the sensitization as an electron transfer process, and triplet sensitization.