Dynamics of Radical Pair Reactions in Micelles

Article abstract of DOI:10.1021/ja00302a001

The time-resolved behavior of sec-phenethyl, cumyl, and diphenylmethyl radicals as radical pairs solubilized in micelles has been observed using pulsed laser photolysis.The decay of the micellized radical pairs consists of a fast component (20-2000*10^-9 s), attributed to reaction within the geminate radical pair, and a slow component (>2000*10^-9 s), attributed to reactions from random encounters of radicals.The extent of geminate pair reaction (micellar cage reaction) depends upon the competition between the rate constants for reaction and diffusive separation.The rate constants for the reaction and diffusion processes are determined and the nature of these processes is discussed.A correlation is found between the extent of fast decay observed in the time-resolved experiments and the extent of cage reaction determined from steady-state photolysis.