Geminate recombination dynamics studied via electron reexcitation: Kinetic analysis for anion CTTS photosystems

Recently, it became practicable to study geminate recombination dynamics of solvated electrons in polar liquids by using short pulses of light to reexcite these electrons back into the conduction band of the liquid and observe a change in the fraction of electrons that escape geminate recombination. In this Letter, the potential of this technique to provide additional insight into the recombination dynamics of electrons generated by charge-transfer-to-solvent (CTTS) photodetachment from monovalent anions in polar liquids is studied theoretically. The resulting expression accounts for the recent results from B.J. Schwartz's group at UCLA for electron photodetachment from Na- in tetrahydrofuran.