Dynamics of radical pair processes in bulk polymers

Abstract

This chapter presents a critical review and a state-of-the-art assessment of the dynamics of the motions and reactions of geminal radical pairs that are generated by photolyses of guest molecules in glassy or rubbery polymer matrices. By virtue of their mode of creation, these radical pairs must reside initially (that is, at their moment of birth) in a common “cage”1 within their polymer host. Specifically excluded from this treatment will be processes of biradicals (i.e., single molecular species containing two radical centers separated by a saturated group),2 radicals that are not spin 1/2, and radical pairs generated from the polymer itself. The dynamics of charge recombination 3 and electron or hole migration4 processes in bulk polymers are not treated here as well.