Journal of the American Chemical Society, Vol.116, No.20, 9182-9186, 1994
Time-Resolved Resonance Raman-Study of the Rate of Separation of a Geminate Ion-Pair into Free Ions in a Medium Polarity Solvent
The rate of separation into free ions of a geminate ion pair generated by photoinduced electron transfer between 9,10-anthraquinone excited to the lowest triplet state and 1,2,4-trimethoxybenzene in 1,1,2,2-tetrachloroethane has been measured at different temperatures by nanosecond time-resolved resonance Raman spectroscopy (TR(3)). The intrinsic activation energy for the separation amounts to 0.04 eV, suggesting that the center-to-center interionic distance in the geminate ion pair is about 7.5 Angstrom. The activation barrier is due to a loss of electrostatic stabilization upon separation to a distance of about 9.5 Angstrom, where a solvent molecule or part of it can interpenetrate to increase the solvation energy. This suggests that the geminate ion pair is a loose ion pair but is not truly solvent separated.
Keywords:PHOTOINDUCED ELECTRON-TRANSFER;PICOSECOND DYNAMICS;CONDENSED-PHASE;DEPENDENCE;EXCIPLEX;CONTACT;STATE