RADICAL PAIR MECHANISM OF CIDEP - COMPARISON OF THE CAGE AND FREE-DIFFUSION MODELS

A simple analytical expression for chemically induced dynamic electron polarization (CIDEP) in geminate recombination of radicals, undergoing relative diffusion in an inter-radical attractive potential, is obtained. The potential is assumed to have a well in which the cage is formed. The expression for CIDEP is derived by the approximate but accurate solution of the stochastic Liouville equation. It is shown that under general conditions the shape of the CIDEP spectra (the dependence of the intensities of hyperfine components on their numbers) is quite universal in the important cases of (1) a short-lived cage; (2) a long-lived cage; (3) rapid free diffusion; (4) slow free diffusion. In all these cases, the CIDEP spectra are calculated and their significant differences, sufficient for experimental identification, are found. © 1990.