Temperature-dependent cage effects from triplet radical pairs generated upon irradiation of 1-(4-methylphenyl)-3-phenyl-2-propanone in polyethylene films.

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The photochemistry of 1-(4-methylphenyl)-3-phenyl-2-propanone (MeDBK) in polyethylene (PE) films of varying crystallinity and at different temperatures has been investigated. Specifically, the selectivity of combination of the initially formed triplet pairs of benzylic radicals derived from irradiation of MeDBK has been used to determine the natures of the PE reaction cavities and how they influence the motions of the radicals. The results indicate that in-cage combinations are favored at lower temperatures and in PE of higher crystallinity. At temperatures significantly above the glass transition of PE, the fraction of radical pairs combining in-cage (F(c)) is independent of the extent of conversion of MeDBK. The data are interpreted according to a structural model that considers the shape, free volume, wall stiffness, and permeability of the reaction cavities and a dynamic model that includes the competition between the rates of in-cage combination and cage escape by the radical pairs. Near the glass transition temperature, F(c) decreases as the temperature is reduced and the data are interpreted using a stochastic model that considers the slow relaxation of the walls of the reaction cavities. The results demonstrate that the cavities afforded by PE can be subtly 'tuned' by temperature changes and microscopic variations in the polymer structure and morphology.