Path integral representation of the reaction rate constant in quantum mechanical transition state theory
- 1 August 1975
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 63 (3) , 1166-1172
- https://doi.org/10.1063/1.431444
Abstract
Feynman’s path integral representation of the Boltzmann operator e −βH is used to express the rate constant of a recently formulated quantum mechanical version of transition state theory. By evaluating the path integral in two separate stages, one is able to interpret the result as a generalization of a model suggested several years ago by Johnston and Rapp for handling the nonseparable aspect of tunneling in transition state theory. A Fourier series expansion of the path integral is also developed, and this approach has promise for direct numerical evaluation of the quantum rate expression.Keywords
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