Phase space dynamics of bimolecular reactions and the breakdown of transition state theory

1987 ◽  
Vol 86 (7) ◽  
pp. 3978-4003 ◽  
Author(s):  
Michael J. Davis
Keyword(s):  
Phase Space ◽  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Bimolecular Reactions ◽  
Space Dynamics

Bimolecular Reactions, Transition-State Theory

2018 ◽  
Author(s):  
Niels Engholm Henriksen ◽  
Flemming Yssing Hansen
Keyword(s):  
Transition State ◽  
Saddle Point ◽  
Transition State Theory ◽  
Classical Mechanics ◽  
Small Degree ◽  
State Theory ◽  
Reaction Coordinate ◽  
Partition Functions ◽  
Bimolecular Reactions ◽  
Activated Complex

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, that is, 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, for example, the F + H2 reaction, and comparisons with results based on quasi-classical mechanics as well as exact quantum mechanics.

scholarly journals ERRATA: TRANSITION STATE THEORY IN EXTENDED PHASE SPACE

1993 ◽  
Vol 07 (21) ◽  
pp. 1407-1407
Author(s):  
H. DEKKER ◽  
A. MAASSEN VAN DEN BRINK
Keyword(s):  
Phase Space ◽  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Extended Phase Space ◽  
Extended Phase

scholarly journals Wigner's dynamical transition state theory in phase space: classical and quantum

Nonlinearity ◽  
2007 ◽  
Vol 21 (1) ◽  
pp. R1-R118 ◽  
Author(s):  
Holger Waalkens ◽  
Roman Schubert ◽  
Stephen Wiggins
Keyword(s):  
Phase Space ◽  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Dynamical Transition
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