Journal of Physical Chemistry A, Vol.105, No.19, 4640-4647, 2001
Temperature and salt addition effect on the micellized radical pairs recombination studied by stimulated nuclear polarization
It was found that the shape of the C-13 stimulated nuclear polarization (SNP) spectra, detected in the photolysis of dibenzyl ketone (DBK) and alpha -methyldeoxybenzoine (MDB), exhibits a noticeable temperature dependence. For the relatively large sodium dodecylsulfate (SDS) micelles, the temperature increase leads to the increase in the line width of SNP spectra, while in the smaller sodium octylsulfate (SOS) micelles the splitting in the SNP spectra decreases. From the comparison of the experimental data with the model calculations based on the numerical solution of the Liouville equation, the influence of the temperature and salt additions on the collision rate of radicals in micelle interior was evaluated. The obtained activation energy of the translational diffusion of small radicals is E-a = 6.7 +/- 0.25 kcal/mol and E-a = 5.6 +/- 0.2 kcal/mol for SDS and SOS micelles, respectively. Additionally, the influence of temperature and salt additions on the lifetime of the micellized radical pairs (RPs) formed in the photolysis of MDB and DBK has been studied experimentally. it is shown that the temperature dependence of the RP lifetime is determined mainly by the changes in the escape rate.