A semiempirical approach has been used to evaluate rate parameters for a three-center decomposition reaction from the point of view of transition state theory, with perfluorodiazirine serving as the prototype molecule. Several activated complex models are considered in which the reaction coordinate is chosen as the 4 N C N bending mode. The consrraints imposed include the principle of concerted bond-order conservation in passing from the initial to the final state, and use is made of empirical bond order-bond length and bond order-force constant relationships. The geometric configuration of the transition state sought is one which conforms with the lowest energy path and is also consistent with the observed entropy of activation. The potential energy of activation is taken as the optimum difference in binding energies (based on the INDO method) between the transition and initial states, and the critical energy is obtained by applying a correction for the zero-point energy difference, derived from normal coordinate analysis. Satisfactory agreement is found in the case of the activated complex model for which the total bond order is conserved and bonds undergoing rupture are assigned a fractional bond order (FBO) of 2 / 3 , derived from the postulate (FBO) = a / B where a ( = 2 ) is the number of bonds breaking, and @( =3) is the number of bonds undergoing change in the ring opening.