Abstract
Quantum yields for the formation of hydrogen and methane in the photolysis of partially deuterated methanethiol (CH 3SD) have been measured at 185 and 254 nm. The sum of the quantum yields of these two products is unity, independent of thiol pressure, at both wavelengths. Adding n-butane or perfluorodimethylcyclobutane causes an increase in the hydrogen quantum yield, a decrease in the methane quantum yield, but no change in the sum of the two. These results are interpreted in terms of a hot atom mechanism involving cleavage of the CS and SD bonds in the parent molecule. Compared with earlier work using CH 3SH, replacing H by D causes a significant increase in the probability of CS cleavage suggesting that the photodissociation process is strongly influenced by the masses of the two species attached to the central sulfur atom.
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