Abstract
Geminate free radical recombination is an important testing ground for current theories of chemical reaction dynamics in liquids. The work described here deals with the recombination of phenyl thiyl radicals in liquid hydrocarbons. Photolysis of diphenyl disulfides using near-ultraviolet light generates thiyl radicals which are detected by picosecond transient absorption spectroscopy. We find that the rate and extent of cage recombination is controlled by solvent viscosity and by the dipole-dipole reorientation energy of a polar radical pair. In moderately viscous liquids such as decalin, for example, cage recombination occurs with a 50% yield and with a half-life of ~150 ps. The influence of both temperature and solvent composition on recombination can be explained by a simple hydrodynamic model of diffusion controlled reactions, using a radiation boundary condition that mimics the reorientation barrier. In polar liquids, cage escape is enhanced by solvation of the radical pair. Based on the interpretation of these experiments it appears that the use of chemical substituents to alter the dipole movement of the radical can be used to study the recombination dynamics in more detail.
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