On the actinic wavelength dependence of OClO photochemistry in solution

Abstract

The role of actinic wavelength in OClO photochemistry was explored using femtosecond pump-probe spectroscopy. Specifically, the evolution of optical density was monitored at probe wavelengths from 267 to 900 nm following 355-nm photoexcitation of OClO dissolved in water and acetonitrile. A central result was that the extent of geminate recombination in a given solvent is dependent on the interplay between the rate of excited-state vibrational relaxation versus the energy needed to overcome the energy barrier to dissociation.