MICROCANONICAL VARIATIONAL THEORY OF RADICAL RECOMBINATION BY INVERSION OF INTERPOLATED PARTITION-FUNCTION .3. CX3O2+NO2(X=H,F,CL)

The title theory (MVIPF) has been applied to the recombinations CH3O2 + NO2, CH3C(O)O2 + NO2, CF3O2 + NO2, CFCl2O2 + NO2, and CCl3O2 + NO2, using for the interfragment potential the so-called extended Rydberg potential. A Gaussian-type switching function was used with a single adjustable constant c for each recombination. The logarithm of the ensemble of c's for all the recombinations fits a linear relationship that in principle allows the determination of the rate constant and its temperature coefficient, for a recombination not yet measured, within a factor of 2. All title recombinations are found to have a negative temperature coefficient that increases in absolute value roughly in proportion to molecular mass.