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
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 
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.
Barrier Height