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

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.

- i Introduction
- ii Theory
- iii Application to Formaldehyde
- iv Concluding Remarks
- v Acknowledgments
- A The microcanonical quantum survival probability
- B RELATION BETWEEN
*f*AND - References