Abstract-The synthesis of a large variety of hyperenergetic molecules such as the 1,2-dioxetanes, u-peroxylactones, 3-imino-l, 2-dioxetanes, benzo-l,4-dioxin dioxetanes, bisdioxetanes, u-pyrone endoperoxides and cyclic peroxalates are presented. The utilization of these unique substances for the thermal generation of electronically excited states is reviewed, with special reference to the total excitation yield ($T+S) and spin state selectivities ($T/$S), The physical and chemical methods for the determination of excitation yields are discussed and scrutinized for their reliability and effectiveness, Mechanistic problems such as energy transfer, heavy atom effects, electron exchange, etc. are analyzed. The biological implications of such "high energy" molecules is emphasized.