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
- Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States)
- Department of Chemistry, Hope College, Holland, Michigan 49423 (United States)
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 nonseparable rovibrational Hamiltonian at the transition state. The overall theory gives a good description of the state-specific rates for the D[sub 2]CO[r arrow]D[sub 2]+CO unimolecular decay; in particular, it describes the dependence of the distribution of rates on total angular momentum [ital J]. Comparison of the experimental values with results of the RM/TST theory suggests that there is mixing among the rovibrational states.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6566807
- Journal Information:
- Journal of Chemical Physics; (United States), Vol. 99:2; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Isotope effects in the photodissociation dynamics of the H sub 3 sup + molecular ion
Question of mode-specificity in unimolecular reaction dynamics
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
MOLECULES
CHEMICAL REACTION KINETICS
ANGULAR MOMENTUM
CONSERVATION LAWS
DYNAMICAL GROUPS
PROBABILISTIC ESTIMATION
KINETICS
REACTION KINETICS
SYMMETRY GROUPS
400201* - Chemical & Physicochemical Properties
661100 - Classical & Quantum Mechanics- (1992-)