New insights into the mechanism of triplet radical-pair combinations. The persistent radical effect masks the distinction between in-cage and out-of-cage processes

Steady-state and laser-pulsed irradiations of dibenzyl ketone (ACOB(0)) and derivatives with a p-methyl or a p-hexadecyl chain (ACOB(1) and ACOB(16), respectively) have been conducted in polyethylene films with 0, 46, and 68% crystallinities. Calculation of the fractions of in-cage combinations of the triplet benzylic radical-pair intermediates based on photoproduct yields, F-c, from ACOB(16) are shown to be incorrect as a result of the kinetic consequences of drastically different diffusion coefficients for the benzyl and p-hexadecylbenzyl radicals. Careful analyses of the transient absorption traces, based upon a new model developed here, allow the correct cage effects to be determined even from ACOB(0). The model also permits the rate constants for radical-pair combinations and escape from their cage of origin to be calculated using either an iterative fitting procedure or a very simple one which requires only k(-CO) and the intensities of the transient absorption immediately after the flash and after the in-cage portion of reaction by the benzylic radicals is completed. Values of the rate constant for decarbonylation of the initially formed arylacetyl radicals, k(-CO), have been measured from the rise portions of the laser-flash transient absorption traces. They confirm the assertion from results in liquid alkane media that decarbonylation rates are independent of microviscosity. The data separate components of a reaction from an (in-cage) "cage effect" and an (out-of-cage) "persistent radical effect" that are responsible for formation of AB-type (i.e., decarbonylated) products. The effects here are a consequence of vastly different rates of diffusion for coreacting A center dot and B center dot benzylic radicals rather than segregation of the radicals in different parts of a hetereogeneous environment (which leads to an excess of AA and BB products). Heretofore, observation of exclusive formation of AB products has been attributed to in-cage combinations of geminate radical pairs. We show that not to be the case here and provide methodologies which may be used for testing the importance of the "persistent radical effect" component of reaction.