Energy transfer processes among the lower vibrational levels in CH3Br have been examined in an attempt to obtain information about the magnitude of the rate constants coupling these levels with one another and coupling ν3 and ν6 to the ground state. We conclude that there is a significant direct deactivation of both ν3 and ν6 to the ground state for CH3Br-CH3Br collisions. The magnitude of V-V rate constants for CH3Br-CH3Br and CH3Br-rare gas interactions are discussed. In the course of these studies, a numerical method has been developed which allows for the determination of kinetic rate constants from measured rates by iterative solution of the coupled set of kinetic equations. Propagation of error from experimental rates to kinetic rate constants has been explicitly considered. The impact of our kinetic analysis and resulting conclusions on previous studies of the methyl halides is also discussed.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry