Summary: Chemical Physics 62 (1981) 387405
North-Holland Publishing Company
VLBRATIONAL ENERGY TRANSFER AND RELAXATJDN PROCESSES IN CHaBr.
A DETAILED KINETIC ANALYSIS OF THE LOWER VIRRATIONAL LEVELS
A.J. OUDERKIRK, V.A. APKARIAN and Eric WEITZ*
Department ofChemistry and Materials Research Cenrer, Norrhwesrem Unicersity, Ecansron. Ihois 60201, US.?
Received 27 May 1981
Energy transfer processes among the lower vibrational levels in CIisBr have been examined in an attempt to obtain
information about the magnitude of the rate constants coup!ing these levels with one another and coupling us and "6 to
the Found state. We conclude that there is a significant direct deactivation of both v3 and vs to the ground state for
CHsBr-CHsBr collisions. The magnitude of V-V rate constants for CHsBr-CHsBr and CHsBr-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.
Vibrational energy transfer in polyatomic
molecules has been the focus of a large number
of experimental and theoretical investigations
[l-9]. A primary goal of the experimental