Calculation on the Microcanonical Unimolecular Rate Constants for the Vibrational-state-selected Reactions

The calculation on the microcanonical unimolecular rate constants for the vibrational state-selected reactions has been studied on the basis of the transition state theory. The quantum mechanic tunneling correction and the coupling correction are involved in the calculations. As examples, the vibrational-state-selected rate constants of the out-of-plane vibration mode for both reactions C-CH(F) -> HC CF and C CF2 -> FC CF have been calculated. The results show that the out-of-plane vibration exhibits a significant degree of mode specificity for both reactions in the low energy regions, but less so in the high energy regions.