Intramolecular dynamics diffusion theory approach to complex unimolecular reactions

A further development of the intramolecular dynamics diffusion theory (IDDT) [J. Chem. Phys. 107, 6204 (1997)] for computing unimolecular reaction rate constants in the IVR-controlled regime is described. The approach is based on Kramers’ energy diffusion theory, with the reaction coordinate taken as the subsystem and the rest of the vibrational modes as the bath. The method provides a practical means of obtaining the rate constants in the IVR-controlled regime at considerable savings of computer time compared to the usual classical trajectory simulations. Its accuracy has been demonstrated in our earlier applications to some simple bond-fission reactions. In the study described here the idea of intrinsic reaction coordinate (IRC) is used to extend the IDDT approach to more complicated systems for which simple reaction coordinates are not easily identifiable. The basic idea is to take the IRC as the subsystem and the transverse vibrational modes as the bath. The method is applied to the unimolecular disso...