Uni molecular Reaction Dynamics on Ab Initio Potential Energy Surfaces

One‐parameter fit versions of unimolecular rate theory for complex elimination and simple bond fission reactions are compared with detailed experiments. The agreement generally is so good that no further extension of this operational version of the theory is required. However, the relation between the fit parameter and properties of the potential surface not always is transparent. The article discusses the implementation of ab initio calculations of the potential by constructing adiabatic channel potential curves. Explicit results for charge‐dipole interactions are presented. SACM‐modified PST applies for selected conditions. Strategies for handling more complex potentials are outlined. The treatment closes the gap between operational fit parameters and potential properties.