Rate constants, reactive flux
This chapter discusses a direct approach to the calculation of the rate constant k(T) that bypasses the detailed state-to-state reaction cross-sections. The method is based on the calculation of the reactive flux across a dividing surface on the potential energy surface. Versions based on classical as well as quantum mechanics are described. The classical version and its relation to Wigner's variational theorem and recrossings of the dividing surface is discussed. Neglecting recrossings, an approximate result based on the calculation of the classical one-way flux from reactants to products is considered. Recrossings can subsequently be included via a transmission coefficient. An alternative exact expression is formulated based on a canonical average of the flux time-correlation function. It concludes with the quantum mechanical definition of the flux operator and the derivation of a relation between the rate constant and a flux correlation function.
Keywords: Wigner's variational theorem, dividing surface, recrossing, flux, transmission coefficient, time-correlation function, flux operator
Oxford Scholarship Online requires a subscription or purchase to access the full text of books within the service. Public users can however freely search the site and view the abstracts and keywords for each book and chapter.
Please, subscribe or login to access full text content.
If you think you should have access to this title, please contact your librarian.
To troubleshoot, please check our FAQs , and if you can't find the answer there, please contact us .