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Abstract:
Magnetic field effects on the hydrogen abstraction reaction of 4-methoxybenzophenone with thiophenol in several solvents of different viscosity have been reported, and the observed magnetic field dependence was explained as caused by the Deltag and a polarized initial triplet radical pair state. The present work reports a quantitative analysis of the data based on a recently derived general analytical formula. It is found that the observed magnetic field dependence can be explained as originating from an unpolarized triplet state, if both the coherent mixing caused by different g values of the two radicals and the incoherent mixing due to spin relaxation are included. Several different expressions for the magnetic field dependence of the longitudinal and transverse relaxation rates were applied. Rather surprisingly, the different models gave almost identical fits. However, the values obtained of the microscopic parameters depended significantly on the model. Physically sensible parameter values were obtained only when the complete magnetic field dependence of the two relaxation times were used. For this model it was found that both the anisotropy factor of the g tensors and the diffusion coefficient agreed with expectations.
