Abstract
Excitation of bromine at wavelengths near the dissociation limit of the B 3Π+0u electronic state is shown to produce substitution and extraction reactions of excited bromine with olefins. These reactions are produced by drastically shortening free-radical chains in contrast to more conventional photochemical experiments which yield addition products only. Shortening of radical chains is accomplished by irradiating a flowing gas mixture in a capillary optical reactor. Wavelength selective photochemical reactions of excited 2P1/2 bromine atoms are found to occur simultaneously with gas phase ground state 2P3/2 atom reactions and with surface reactions. Evidence for reactions of electronically excited molecules of bromine in the B 3Π+0u state is also found.
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