The luminescence that is obsd. under gas phase photolytic deposition conditions is studied for Cr(hfac)3, Ni(hfac)2, and Pt(hfac)2. This luminescence is analyzed under a variety of conditions, including the relatively high pressures of an evacuated gas cell and the collision-free conditions of a mol. beam. The effects of inert buffer gas are also studied. Features in these spectra indicate that, in general, multiple photolysis processes occur. Some simple fragments that are produced from these compds. are identified, including bare metal atoms (Ni, Cr), metal monofluorides (NiF, CrF), CH (in the case of Ni(hfac)2), and metal carbide from Pt(hfac)2. It is postulated that the difference in the obsd. photofragmentation pathway in the case of Pt is due to sigma bonding to the Beta C of the hfac moiety as opposed to the bidentate bonding of the other 2 metals. Possible mechanisms are presented. Detailed anal. of the spectra allows characterization of the internal energy of the Pt carbide photofragment.