Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide

Details Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide

2005-01-18

arxiv.org/abs/physics/0501098v1

Chem. Phys. Lett. 383 (2004) 481

Physics

Chemical Physics

14 pages, 1 figure

Scientific paper

The picosecond dynamics of hydroxyl radicals generated in 200 nm photoinduced dissociation of aqueous hydrogen peroxide have been observed through their transient absorbance at 266 nm. It is shown that these kinetics are nearly exponential, with a decay time of ca. 30 ps. The prompt quantum yield for the decomposition of H2O2 is 0.56, and the fraction of hydroxyl radicals escaping from the solvent cage to the water bulk is 64-68%. These recombination kinetics suggest strong caging of the geminate hydroxyl radicals by water. Phenomenologically, these kinetics may be rationalized in terms of the diffusion of hydroxide radicals out of a shallow potential well (a solvent cage) with an Onsager radius of 0.24 nm.

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