Comprehensive kinetics and reaction thermochemistry have been predicted for the four radical association reactions forming the C 2 -C 4 n-perfluoroalkanes, as well as the bimolecular well-skipping reaction over the C 4 F 10 well. A high-level correction potential for CASPT2/cc-pVDZ direct dynamics potential evaluations in VRC-TST has been developed for CF 3 + CF 3 based on spin-splitting approaches, and implemented in the calculation of high-pressure-limit rate coefficients. ANL0/ANL1-like composite quantum chemistry methodologies have been used to compute enthalpies of formation for the target species using the CBH0, CBH1, CBH2, and CBH3 rungs of the error-cancelling reaction schemes. This combination of ANL schemes and CBH schemes provide low uncertainty in the computed enthalpies of formation.