New analytical potential energy surface for the F(2P)+CH4 hydrogen abstraction reaction: kinetics and dynamics.
A new potential energy surface for the gas-phase F(2P)+CH4 reaction and its deuterated analogues is reported, and its kinetics and dynamics are studied exhaustively. This semiempirical surface is completely symmetric with respect to the permutation of the four methane hydrogen atoms, and it is calibrated to reproduce the topology of the reaction and the experimental thermal rate constants. For the kinetics, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wide temperature range, 180-500 K. The theoretical results reproduce the experimental variation with temperature. The influence of the tunneling factor is negligible, due to the flattening of the surface in the entrance valley, and we found a direct dependence on temperature, and therefore positive and small activation energies, in agreement with experiment. Two sets of kinetic isotope effects were calculated, and they show good agreement with the sparse experimental data. The coupling between the reaction coordinate and the vibrational modes shows qualitatively that the FH stretching and the CH3 umbrella bending modes in the products appear vibrationally excited. The dynamics study was performed using quasi-classical trajectory calculations, including corrections to avoid zero-point energy leakage along the trajectories. First, we found that the FH(nu',j') rovibrational distributions agree with experiment. Second, the excitation function presents an oscillatory pattern, reminiscent of a reactive resonance. Third, the state specific scattering distributions present reasonable agreement with experiment, and as the FH(nu') vibrational state increases the scattering angle becomes more forward. These kinetics and dynamics results seem to indicate that a single, adiabatic potential energy surface is adequate to describe this reaction, and the reasonable agreement with experiment (always qualitative and sometimes quantitative) lends confidence to the new surface.
Espinosa-García
J
J
Departamento de Química Física, Universidad de Extremadura, 06071 Badajoz, Spain. joaquin@unex.es
Bravo
J L
JL
Rangel
C
C