Influence of Molecular Parameters on Rate Constants of Thermal Dissociation/Recombination Reactions: The Reaction System CF 4 ⇄ CF 3 + F.

The possibilities to extract incompletely characterized molecular parameters from experimental thermal rate constants for dissociation and recombination reactions are explored. The reaction system CF 4 (+M) ⇄ CF 3 + F (+M) is chosen as a representative example. A set of falloff curves is constructed and compared with the available experimental database. Agreement is achieved by minor (unfortunately not separable) adjustments of reaction enthalpy and collisional energy transfer parameters.