Non-linear dynamics in photochemistry

Abstract The rate law of an elementary photochemical reaction: A → B ( hv ), contains 4 independent factors: the quantum yield, the photon flux, the concentration of the photosensitive substrate and the photokinetic factor. This type of reaction will always slow down. However, by increasing one of these 4 factors artificially, the reaction can be made to speed up. Using kinetic models comprising one or more photochemical reactions, we show that appropriate coupling between two or more elementary processes gives rise to a cooperative effect. This effect increases one or more of these 4 factors, and makes the coupled photochemical model bistable in a CSTR. The values of the parameters for which one observes bistability are experimentally realistic. One of these models provides a simplified simulation of the stages underlying the bistable photochemical behavior of the TPID/CHCl 3 , system.