Microcanonical variational theory of radical recombination by inversion of interpolated partition function. Part 2.—CX3+ O2(X = H, F, Cl)

Abstract

The title theory (MVIPF) has been applied to the recombinations of O₂ with the radicals CH₃, CF₃, CF₂Cl, CFCl₂ and CCl₃ and compared, with generally good results, to experimental data which are available for all radicals but one (CF₂Cl). In particular, MVIPF, which is based on minimum information and uses an adjustable parameter (c) in a Gaussian-type switching function, correctly reproduces the fact that the recombination CH₃+ O₂ has a positive temperature coefficient, while all the other radical recombinations have a negative temperature coefficient. Consolidated results by MVIPF for the nine recombination reactions for which experimental data are available (the title reactions, plus CH₃+ H, CH₃+ CH₃, CH₂Cl + CH₂Cl, CHCl₂+ CHCl₂, CCl₃+ CCl₃), yield a linear relation for a function of the logarithm of c, which in principle allows one to predict a recombination rate constant in a series of similar reactions within a factor of two.