Geminate recombination kinetics of solute radical ions. Singlet excited state formation in cyclohexane solutions of biphenyl

Transient absorption spectra of the solute anion, cation and triplet state and the solute fluorescence in the pulse radiolysis of 0.1 mole 1^-1 biphenyl in cyclohexane were observed on a nanosecond timescale longer than 1 ns after a 20 ps pulse. The formation of the solute excited singlet state is mainly due to the geminate ion recombination reaction even in the high concentrated solutions. The decay of the solute ions obeys the reciprocal square root dependence on time longer than 10 ns from the end of a 10 ps pulse. The slope of this reciprocal square root plots agrees with the literature value on a longer timescale obtained by microwave absorption. The yield of free ions obtained from the intercept of the slope agrees also with the literature values obtained by the field clearing method. Ratio of the formation rate of the solute excited triplet state to the decay rate of the solute anion changes in a time range between 5 and 20 ns. It is very well correlated with a theoretical calculation of spin correlation decay of the germinate ion pairs by Brocklehurst, although the formation of the solute triplet state was observed even on a timescale shorter than 5 ns from the end of a 20 ps pulse, where loss of spin correlation is negligibly small.