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Theories of Molecular Reaction DynamicsThe Microscopic Foundation of Chemical Kinetics$
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Niels E. Henriksen and Flemming Y. Hansen

Print publication date: 2008

Print ISBN-13: 9780199203864

Published to Oxford Scholarship Online: January 2010

DOI: 10.1093/acprof:oso/9780199203864.001.0001

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Bimolecular reactions, transition-state theory

Bimolecular reactions, transition-state theory

Chapter:
(p.139) 6 Bimolecular reactions, transition-state theory
Source:
Theories of Molecular Reaction Dynamics
Author(s):

Niels E. Henriksen

Flemming Y. Hansen

Publisher:
Oxford University Press
DOI:10.1093/acprof:oso/9780199203864.003.0006

This chapter discusses an approximate approach — transition-state theory — to the calculation of rate constants for bimolecular reactions. A reaction coordinate is identified from a normal-mode coordinate analysis of the activated complex, i.e. the supermolecule on the saddle-point of the potential energy surface. Motion along this coordinate is treated by classical mechanics and recrossings of the saddle point from the product to the reactant side are neglected, leading to the result of conventional transition-state theory expressed in terms of relevant partition functions. Various alternative derivations are presented. Corrections that incorporate quantum mechanical tunnelling along the reaction coordinate are described. Tunnelling through an Eckart barrier is discussed and the approximate Wigner tunnelling correction factor is derived in the limit of a small degree of tunnelling. It concludes with applications of transition-state theory to, e.g. the F + H2 reaction, and comparisons with results based on quasi-classical mechanics as well as exact quantum mechanics.

Keywords:   activated complex, normal-mode coordinates, reaction coordinate, transition-state theory, partition function, tunnelling, tunnelling factor

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