Quantum Theory for the Unimolecular Rate Constant
- 15 July 1966
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 45 (2) , 491-495
- https://doi.org/10.1063/1.1727595
Abstract
A formal quantum theory for the unimolecular rate constant is presented. This theory is an elaboration on an earlier paper by Wilson and Thiele. The theory treats the unimolecular breakdown quantum mechanically, but retains two classical-like assumptions concerning the collision mechanism and the criteria for reaction. A model calculation suggests that these assumptions can be used if ω≪kT/h. Some arguments are also presented which suggest this same limit of applicability for the general theory.Keywords
This publication has 12 references indexed in Scilit:
- Classical Unimolecular Rate Theory. III. Effect of Initial Conditions on Lifetime DistributionsThe Journal of Chemical Physics, 1965
- Quantum Uncertainty in the Time of a CollisionThe Journal of Chemical Physics, 1965
- Quantum-Mechanical Formulation of a Strong Collision Theory of Unimolecular RatesThe Journal of Chemical Physics, 1964
- Classical Unimolecular Rate Theory. Rotating Anharmonic Diatomic MoleculesJournal of the American Chemical Society, 1962
- Monte Carlo Calculation of Triatomic Dissociation Rates. I. N2O and O3The Journal of Chemical Physics, 1962
- Comparison of the Classical Theories of Unimolecular ReactionsThe Journal of Chemical Physics, 1962
- Cubic Potential Surfaces in the Transition-State Theory of Unimolecular ReactionsThe Journal of Chemical Physics, 1961
- On the Dissociation of Polyatomic MoleculesThe Journal of Chemical Physics, 1960
- New Formulation of Gaseous Unimolecular Dissociation RatesThe Journal of Chemical Physics, 1956
- The exact transition probabilities of quantum-mechanical oscillators calculated by the phase-space methodMathematical Proceedings of the Cambridge Philosophical Society, 1949