INTERPLAY OF THEORY AND EXPERIMENT IN THE DETERMINATION OF TRANSITION-STATE STRUCTURE

The idea of a transition state is fundamentally a theoretical one associated with the properties of a saddle-point region of a potential-energy hypersurface describing a chemically reacting system. Experimentally, however, a transition state is usually a phenomenological concept associated with a manner of interpretation of kinetic data. The two views do not always coincide! Some recent attempts to bridge the gap between theory and experiment in the areas of structure-reactivity correlations and kinetic isotope effects are discussed, and it is argued that computational modelling will enable meaningful interpretation of experimental data in terms of transition-state structure.