The relative amounts of Cl(P-2(3/2)) [Cl], Cl(P-2(1/2)) [Cl*], H, and HCl produced by 193 nm photodissociation of CH3CF2Cl and CH3CFCl2 were studied by a laser pump-and-probe technique. An excimer laser photodissociated the parent molecules and a frequency doubled tunable dye laser probed the photofragments via (2+1) resonantly enhanced multiphoton ionization coupled with a time-of-flight mass spectrometer. Only atomic products were observed; no HCl was found. The profiles were well fitted to Gaussians. The Cl*/Cl branching ratios were almost identical, 0.18+/- 0.04 and 0.16+/- 0.04, while the H/(Cl+Cl*) ratios were 0.67+/- 0.21 and 0.18+/- 0.07, for CH3CF2Cl and CH3CFCl2, respectively. The mechanism for the production of the atomic species is discussed. (C) 1997 American Institute of Physics. [S0021-9606(97)03344-8].