Basic parameters of the generalized Rose-Fowler-Weisberg theory were experi
mentally determined for polystyrene. The obtained data were used to compreh
ensively analyze the evolution of geminate pairs in this polymer. It was sh
own that the generation of the prompt component of radiation-induced conduc
tivity occurs by the trapping mechanism with two charge carrier states invo
lved, the quasi-free and trapped. This generation under equilibrium transpo
rt conditions (diffusivity and mobility of carriers are constant) reportedl
y ensured by the geminate recombination itself was not observed in a real e
xperiment. With allowance for dispersive transport of holes (the major carr
iers), the lifetime of geminate pairs were found to be as long as a few hun
dred of milliseconds at 300 K. The published data on the formation and deca
y kinetics in doped polystyrene upon its pulse radiolysis or photolysis wer
e thoroughly analyzed. It was shown that, at ultrashort times before locali
zation of generated carriers, the contribution of electrons to the observed
conductivity prevails, although the basic contribution is made by holes in
later times.