While the Pitzer model had been used in the past with great success for degenerate internal motions, e.g., transitional bending motions in the recombination of hydrogen and methyl radicals, simpler models are often used in the treatment of nondegenerate modes, such as the transitional bending motions in the recombination reaction of hydrogen and choloromethyl radicals. In this work, highly detailed analysis of the Pitzer free rotor treatment for nondegenerate internal motions is presented. The addition reaction of a chlorine radical with 1,1,-dichloroethylene is used here for illustrative purposes. The reaction proceeds in two steps: the reactants reach a bridged intermediate that can dissociate back to reactants or yield the *C2H2Cl3 adducts. Only the long-range part of the reaction was investigated in this paper. Electronic structure calculations were performed at the UQCISD(T)/6-31G**//UMP2/6-31G** level of theory, and canonical variational transition state theory rate constants were computed. In conclusion, it is shown that two different pathways lead to the bridged intermediate. Consideration of the forward and backward rate constants demonstrated that the more direct route to the bridged intermediate is favored kinetically.