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Intramolecular and Unimolecular Dynamics of Reaction Intermediates

The intramolecular and unimolecular dynamics of reaction intermediates is determined by the coupling between modes and the efficiency of intramolecular vibrational energy redistribution (IVR). If IVR is complete and occurs on a time scale much shorter than that for the unimolecular reaction, RRKM theory may be used to calculate the intermediates lifetime and the energy on distribution at the dissociation transition state. It is important to understand what properties lead to non-RRKM kinetics for reaction intermediates. The isomerization dynamics of trimethylene (see Figure) is non-RRKM.