Transition-State Models and Hydrogen-Isotope Effects

Abstract

The transition-state theory of chemical kinetics, coupled with relatively crude methods of constructing potential-energy surfaces for reacting systems, has great utility in the forecasting of kinetic properties. In particular, it permits prediction of the effect of isotopic substitution on rate constants, and comparison of these predictions with experimental data provides a particularly sensitive test for the combination of potential-energy surface and transition-state theory. More rigorous tests of each of these factors depend on future developments in quantum chemistry, in studies of chemical reactions in molecular beams, and in detailed trajectory calculations of scattering processes.