Ab initio and direct quasiclassical-trajectory study of the F+CH4→HF+CH3 reaction -: art. no. 214305

We present an electronic structure and dynamics study of the F+CH(4)-> HF+CH(3) reaction. CCSD(T)/aug-cc-pVDZ geometry optimizations, harmonic-frequency, and energy calculations indicate that the potential-energy surface is remarkably isotropic near the transition state. In addition, while the saddle-point F-H-C angle is 180 degrees using MP2 methods, CCSD(T) geometry optimizations predict a bent transition state, with a 153 degrees F-H-C angle. We use these high-quality ab initio data to reparametrize the parameter-model 3 (PM3) semiempirical Hamiltonian so that calculations with the improved Hamiltonian and employing restricted open-shell wave functions agree with the higher accuracy data. Using this specific-reaction-parameter PM3 semiempirical Hamiltonian (SRP-PM3), we investigate the reaction dynamics by propagating quasiclassical trajectories. The results of our calculations using the SRP-PM3 Hamiltonian are compared with experiments and with the estimates of two recently reported potential-energy surfaces. The trajectory calculations using the SRP-PM3 Hamiltonian reproduce quantitatively the measured HF vibrational distributions. The calculations also agree with the experimental HF rotational distributions and capture the essential features of the excitation function. The results of the SRP semiempirical Hamiltonian developed here clearly improve over those using the two prior potential-energy surfaces and suggest that reparametrization of semiempirical Hamiltonians is a promising strategy to develop accurate potential-energy surfaces for reaction dynamics studies of polyatomic systems.