Abstract
The photolysis of aqueous C1O2 has been studied with a new femtosecond transient absorption spectrometer, allowing absorbance changes as small as ΔA͌ 1 × 10-4 to be recorded with a time resolution of 150 fs. ClO2 was photolyzed at 390 nm and the ultrafast formation and decay of photoproducts were monitored from 230 nm to 78 nm, using either harmonics of the 780 nm pulses or a white light continuum. The main photolytic product, ClO + O, is formed with a quantum yield of 0.9, but disappears through a fast geminate recombination, producing vibrational excited C1O2 in the electronic ground state. The hot ClO, subsequently cools down in 10 ps. In addition to ClO + O, Cl + O2 is formed, with a quantum yield of 0.1 within the first 10 ps of the photolysis pulse, thus indicating the absence of the expected long-lived ClOO species. Using a simple model including the vibrational cooling of C1O2 and the absorbance of aqueous Cl we are able to account for the experimental observations.
© 1997 Optical Society of America
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