Picosecond absorption spectroscopy has been employed in the study of the solvent dynamics of 1,2,4,5-tetracyanobenzene/biphenyl derivative radical ion pairs, and the resulting rates of radical ion pair separation are faster in acetonitrile than in dichloromethane.
In an effort to account quantitatively for such solvent effect on the rate of radical ion pair separation, an equation for the rate of radical ion pair separation is introduced, in which the rate depends exponentially on the electrostatic interaction energy in the radical ion pair.
In our analysis of the types of electrostatic interaction energy, the electrostatic energy based on the conducting spheres in dielectric continuum was chosen, and the rate equation employing this electrostatic energy provided information on the distance of radical ion pair separation and solvation energy of the radical ion pair, thereby providing quantitative explanation for the observed solvent effect on the rate of radical ion pair separation.