Here, a new implementation for calculating canonical variational rate constants is introduced and tested against methanol dissociation rate constants and the (high pressure) radical recombination reaction, CH3 + OH → CH3OH. Reaction paths are described at the CASSCF level, with energy corrections at MRMP2. Molecular properties for both stationary and non-stationary points along the reaction path are used for the calculation of rate constants. Different models for the low vibrational frequencies are discussed: harmonic oscillator and free rotor models. The CH3 + OH → CH3OH recombination rate constants are determined from dissociation rate constants and equilibrium constants. Our calculated rate constants agree with previously reported data for these reactions, suggesting the good performance of our implemented code in calculating canonical variational rate constants. The rate expressions are suggested: as: kdis (T) = 8.42 × 10+16 × e−96.18/RT and krec (T) = 2.05 × 10−10 × (T/298)−0.24 × e−0.30/RT, in units s−1 and cm3 molecule−1 s−1, respectively, and over the temperature range 300–2000 K, with activation energies in kcal/mol. © 2012 Wiley Periodicals, Inc.