Theoretical Analysis of Experimental Probes of Dynamics of Intramolecular Vibrational Relaxation
The phenomenon of intramolecular vibrational relxation is postulated to play a central role in the description of unimolecular reaction processes of polyatomic molecules. For instance, the famous RRKM theory is generally presented as being predicated on the assumption that vibrational energy is rapidly randomized among the different vibrational degrees of freedom on time scales which are rapid compared to the decomposition times of these molecules.1, 2 A number of different theoretical approaches have been undertaken to understand better the phenomena of vibrational energy scrambling in molecules. Other talks at this conference discuss the transition from quasiperiodic to stochastic behavior in classical mechanical descriptions of vibrational energy in molecules with the hopes that in an as yet undefined fashion this is somehow relevant to the description of energy randomization processes occurring in real molecules under experimental conditions. This lecture is concerned with providing a theoretical basis for understanding recent experiments on intra-molecular vibrational relaxation.
KeywordsZeroth Order Vibrational Energy Intermediate Case Vibrational Relaxation Double Exponential Decay
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- 1.P. J. Robinson and K. A. Holbrook, Unimolecular Reactions, Wiley, Newufork, 1972.Google Scholar
- 5.J. B. Hopkins, D. E. Powers and R. E. Smalley, J. Chem. Phys. 71 3886 (1979); 72, 2905 (E) (1980); (b) J. B. Hopkins, D. E.Powers, S. Mukamel, and R. E. Smalley, J. Chem. Phys. 72:, 5049 (1980); (c) J. B. Hopkins, D. E. Powers and R. E. Smalley, J. Chem. Phys. 73, 683 (1980).ADSCrossRefGoogle Scholar
- 11.J. W. Perry and A. H. Zewail, J. Chem. Phys. 70, 582 (1979); Chem. Phys. Lett. 65, 31 (1980).Google Scholar
- 17.T. F. Deutch and S. J. Brueck, Chem. Phys. Lett. 54, 258 (1978); D. S. Frankel, J. Chem. Phys. 65, 1696 (1976).Google Scholar
- 19.S. Mukamel and J. Jortner, in Excited States, ed. E. C. Lim, Academic Press, New York, 1977.Google Scholar
- 24.S. A. Rice, this volume.Google Scholar
- 27.K. F. Freed (unpublished); G. Atkinson (private communication); S. Leach (private communication).Google Scholar