Two important fluoropolymers, polytetrafluoroethylene [PTFE-(C2F4)(N)] and polyvinylidene fluoride [PVDF-(C2H2F2)(N)], respond to 157-nm laser radiation in dramatically different ways. At fluences sufficient to produce rapid etching, the volatile emissions from PTFE are dominated by (CF2)(N) fragments. The velocities of the fastest (CF2)(N) molecules at each mass are consistent with kinetic energies on the order of an electron volt-and change little with fluence. This fluence independence suggests that the velocities are not affected by collisions after emission. To account for the high kinetic energies and the unusual, half-monomer mass distribution, we propose that these fragments are produced by photochemical scission of the polymer backbone, and that a fraction of the excitation energy is delivered to each fragment as kinetic energy. In contrast, the principle neutral species from PVDF is HF. HF is produced by the scission of C-F bonds, followed by chemical reactions with nearby hydrogen. This process is accompanied by the conjugation of backbone C-C bonds. The photochemical cleavage of C-C bonds in PTFE and C-F bonds in PVDF is consistent with the lower C-C bond energy of PTFE. (C) 2009 Elsevier B. V. All rights reserved.