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Cage effect

In chemistry, the cage effect (also known as geminate recombination) describes how the properties of a molecule are affected by its surroundings. First introduced by James Franck and Eugene Rabinowitch in 1934, the cage effect suggests that instead of acting as an individual particle, molecules in solvent are more accurately described as an encapsulated particle. The encapsulated molecules or radicals are called cage pairs or geminate pairs. In order to interact with other molecules, the caged particle must diffuse from its solvent cage. The typical lifetime of a solvent cage is 10-11 seconds. Many manifestations of the cage effect exist.

Cage recombination efficiency
The cage effect can be quantitatively described as the cage recombination efficiency Fc where: :F_c = k_c/(k_c + k_d) It is reported that the cage effect will increase with an increase in radical size and a decrease in radical mass. == Initiator efficiency ==
Initiator efficiency
In free radical polymerization, the rate of initiation is dependent on how effective the initiator is. Low initiator efficiency, ƒ, is largely attributed to the cage effect. The rate of initiation is described as: :R_i = 2fk_d[I] where Ri is the rate of initiation, kd is the rate constant for initiator dissociation, [I] is the initial concentration of initiator. Initiator efficiency represents the fraction of primary radicals R·, that actually contribute to chain initiation. Due to the cage effect, free radicals can undergo mutual deactivation which produces stable products instead of initiating propagation – reducing the value of ƒ. == See also ==
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