Electron photodetachment from aqueous anions. 2. Ionic strength effect on geminate recombination dynamics and quantum yield for hydrated electron

In concentrated solutions of NaClO4 and Na2SO4, the quantum yield for free electron generated by detachment from photoexcited anions (such as I-, OH-, ClO4-, and SO32-) linearly decreases by 6-12% per 1 M ionic strength. In 9 M sodium perchlorate solution, this quantum yield decreases by roughly 1 order of magnitude. Ultrafast kinetic studies of 200 nm photon induced electron detachment from Br-, HO-, and SO32- and 228 nm photodetachment from I- suggest that the yield of thermalized, solvated electron does not change in these solutions; rather, the ionic strength effect originates in more efficient recombination of geminate pairs. Within the framework of the recently proposed mean force potential (MFP) model of charge separation dynamics in such photosystems, the observed changes are interpreted as an increase in the short-range attractive potential between the geminate partners. Association of sodium cation(s) with the electron and the parent anion is suggested as the most likely cause for the observed modification of the MFP. Electron thermalization kinetics suggest that the cation associated with the parent anion (by ion pairing and/or ionic atmosphere interaction) is passed to the detached electron in the course of the photoreaction. The precise atomic-level mechanism for the ionic strength effect is presently unclear; any further advance is likely to require the development of an adequate quantum molecular dynamics model.