Chemistry of nuclear recoil¹⁸f atoms. vi. approximate energetics and molecular dynamics in ch₃cf₃

Energetics and molecular dynamics results are reported from an extensive set of high energy recoil ¹⁸F experiments with CH₃CF ₃. Based upon thermochemical evidence alone, substantial fractions of the primary hot F-for-H, F-for-CH₃, and F-for-CF₃ reaction products are indicated to involve minimum excitation energies of 7.9±0.2, 9.3±0.1, and 3.5±0.2 eV, respectively. The primary F-for-F reaction products in CH³CF₃ do not exhibit unimolecular decomposition via a carbon-carbon bond scission mode in apparent violation of RRKM theoretical predictions. The primary F-for-H products decompose both via O elimination of HF and via carbon-carbon bond scission in apparent accord with theory. More than one kind of microscopic dynamics is involved in the primary hot F-for-H and F-for-CH₃ processes in CH₃CF₃ and in the primary hot F-for-F process in CF ₄. Direct, concerted, and collusive dynamics are required for the higher energy reaction modes for these processes.