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The energy gap dependence of the charge recombination (CR) rate constant ( k~) of geminate ion pairs produced by exciting the ground state charge transfer complexes adsorbed on the porous glass was investigated by means of picosecond laser photolysis. The same energy gap dependence of ~C R as observed in polar solutions by Mataga et al. was also found in the adsorbed systems. Evidently, the present result indicates that not the polar solvent dynamic motions but the intramolecular high-frequency quantum modes in the ion pair predominate in the CR process of these ion pairs. The dielectric constant experienced by the ion pairs on the porous glass was estimated to be ca. 4-5.

An extremely long-lived (>>8 h) charge-separated species was observed following photoinduced electron transfer in poly(N-vinylcarbazole) coadsorbed with 1,2,4,.5-tetracyanobenzene as an electron acceptor on a macroreticular resin, Amberlite XAD-8, at room temperature. The formation and deactivation of the longlived charge-separated states were discussed from the viewpoints of the effective hole transfer via the carbazolyl groups along the polymer chain to result in the ion pair with rather large interionic distance and the longdistance back electron transfer in the ion pair.

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