VARIATIONAL THEORY OF REACTION RATES,
Abstract
The variational theory of reaction rates is reviewed and used to derive a general expression for the reaction rate constant corresponding to the flow of representative points in phase space through any trial surface separating reactants and products. It is shown that unimolecular decay theory, absolute reaction rate theory, available energy theory, and statistical reaction rate theory are all special cases of the variational theory corresponding to different choices of the trial surface. Applications of the theory to three-body recombination and dissociation are considered in detail and expressions for the available energy, three-body collision, Wigner and barrier-rate constants derived and compared. Methods of correcting the theory using Monte Carlo trajectory calculations are discussed. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1966
- Accession Number
- AD0629937
Entities
People
- James C. Keck
Organizations
- Massachusetts Institute of Technology