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JOURNAL OF CHEMICAL PHYSICS; 99, 950 (1993).
all rights reserved.


A Random Matrix / Transition State Theory for the Probability
Distribution of State-Specific Unimolecular Decay Rates:
Generalization to Include Total Angular Momentum
Conservation and Other Dynamical Symmetries

Rigoberto Hernandez, William H. Miller, and C. Bradley Moore

Department of Chemistry, University of California, and
Chemical Sciences Division, Lawrence Berkeley Laboratory
Berkeley, California 94720

and

William F. Polik

Department of Chemistry, Hope College
Holland, Michigan 49423

Abstract:

A previously developed random matrix / transition state theory (RM/TST) model for the probability distribution of state-specific unimolecular decay rates has been generalized to incorporate total angular momentum conservation and other dynamical symmetries. The model is made into a predictive theory by using a semiclassical method to determine the transmission probabilities of a non-separable rovibrational Hamiltonian at the transition state. The overall theory gives a good description of the state-specific rates for the tex2html_wrap_inline733 unimolecular decay; in particular, it describes the dependence of the distribution of rates on total angular momentum J. Comparison of the experimental values with results of the RM/TST theory suggests that there is mixing among the rovibrational states.





hernandez@chemistry.gatech.edu