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The use of lasers with jet-cooled samples has improved energy and angular momentum resolution for the reactant and time resolution for the rate constant by orders of magnitude. The resolution of product quantum states has added a new dimension to unimolecular dynamics. In the past, the geometry, barrier height and vibrational frequencies of the transition state in RRKM theory were adjusted to fit thermal unimolecular reaction rate data. There have been successful quantitative tests of the ability of ab initio theory to calculate transition state geometries accurately and barrier heights to a few kJ/mol for simple molecules. Predicted frequencies tend to be somewhat too high for the softest modes which are of most importance in determining rates; however, the basic normal modes and sequence of frequencies seem to be correctly predicted. RRKM theory can be used with ab initio results to predict rate constants to within a factor of two or three and may be used for quantitative extrapolation to conditions not accessible in the laboratory but important in practical situations. Experiments on single molecular eigenstates have revealed quantum statistical fluctuations in rates which are predicted quantitatively in the appropriate extension of RRKM theory. Many experiments seeking to demonstrate non-statistical or non-RRKM dynamics have demonstrated the very wide range of applicability of the RRKM model. A few such experiments have demonstrated a lack of complete vibrational energy randomization in a reactant molecule. Dynamical theory has provided an exact quantum analog to RRKM theory which will combine with future experiments to define the extent to which quantized motion along the reaction coordinate and coupling between the reaction coordinate and vibrational degrees of freedom at the transition state are important. 42 refs., 11 figs

Energy states and energy flow near the transition states of unimolecular reactions