The structural degradation of polytetrafluoroethylene (PTFE) upon irradiation with MeV alpha (a) particles is accompanied by the proliferation of hydrogenated and oxygen-functionalized fluorocarbon species. In this article, we explore the origin of monoxide- and dioxide-functionalized fluorocarbon species that emerge upon a particle irradiation of PTFE. Samples of neat PTFE were irradiated to a doses in the range of 10(7)-5 X 10(10) rad using 5.5 MeV He-4(2+) ions produced in a tandem accelerator. Static time-of-flight secondary-ion-mass spectrometry (TOF-SIMS), using a 20 keV C-60(+) source, was employed to probe chemical changes as a function of a particle irradiation. Chemical images and high-resolution mass spectra were collected in both the positive and negative polarities. Residual gas analysis, utilized to monitor the liberation of molecular gases during a particle irradiation of the PTFE in vacuum, is discussed in relationship to the TOF-SIMS data. (c) 2006 American Vacuum Society.