Potential energy surface for the F(2P(3/2),2P(1/2)) + CH4 hydrogen abstraction reaction. kinetics and dynamics study.
A modified and recalibrated potential energy surface (PES) is reported for the gas-phase F(2P(3/2),2P(1/2)) + CH4 reaction and its deuterated analogue. This semiempirical surface is completely symmetric with respect to the permutation of the four methane hydrogen atoms and is calibrated with respect to the updated experimental and theoretical stationary point properties and experimental thermal rate constants. To take into account the two spin-orbit electronic states of the fluorine atom, two versions of the surface were constructed, the PES-SO and PES-NOSO surfaces, which differ in the choice of the zero reference level of the reactants. On both surfaces, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wide temperature range, 180-500 K. While the PES-SO surface overestimates the experimental rate constants, the PES-NOSO surface shows a better agreement, reproducing 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. The kinetic isotope effects calculated showed good agreement with the sparse experimental data at 283 and 298 K. Finally, on the PES-NOSO surface, other dynamical features, such as the coupling between the reaction coordinate and the vibrational modes, were analyzed. It was found qualitatively that the FH stretching and the CH3 umbrella bending modes in the products appear vibrationally excited. These kinetics and dynamics results seem to indicate that a single, adiabatic PES is adequate to describe this reaction.
Rángel
Cipriano
C
Departamento de Química Física, Universidad de Extremadura, 06071 Badajoz, Spain.
Navarrete
Marta
M
Espinosa-García
J
J