The Hammond postulate: A quantitative interpretation

The Hammond postulate is considered in terms of the model of intersecting parabolas. It is shown that, in radical detachment reactions of the type X _f ^· + HX _i → X _f H + X _i ^· with a symmetrical reaction center X _i …H…X _f , the H atom in the transition state is equidistant from the X _i and X _f atoms if the enthalpy of the reaction ΔH = 0. The X _i …H distance increases and the X _f …H distance decreases linearly as ΔH grows. The dependence remains linear over the range ΔH _min ≤ ΔH ≤ H _max. The same result was obtained in quantum-chemical calculations for reactions of the type R _f ^· + R _i H. In reactions of the type X^· + HY → XH + Y^· with an asymmetric reaction center X…H…Y, the X…H and Y…H interatomic distances in the transition state at ΔH = 0 depend on the force constants and lengths of the X-H and Y-H bonds. The Y…H distance increases and the X…H distance decreases linearly as ΔH grows. A similar picture is observed in the model of intersecting Morse curves, where the dependence of interatomic distances on ΔH in the transition state is nonlinear. Equations describing interatomic distances in the transition state as functions of the enthalpy of the reaction are presented.