We present results on `site-specific' H-atom production in photolysis experiments conducted under collisionless conditions. H and D atoms are used as labels to investigate the site(s) at which C-H (or C-D) bond cleavage occurs in a variety of haloalkane systems. Experiments using two photolysis lasers clearly indicate that photon absorption by an intermediate, presumably an alkyl radical, is important in many of the systems studied. The site(s) (e.g., $alpha@, $beta@, or $gamma@) at which C-H (or C-D) bond cleavage occurs is dependent not only on the nature of the molecule, but also on the photolysis wavelength. As a diagnostic tool, H- and D-atom Doppler spectroscopy allows us to gain insight into the energetics associated with the various dissociation processes. Our overall aim is to gain a further understanding of the photolysis properties of a variety of simple molecules and their associated radicals.
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