scholarly journals Reaction rate theory: summarising remarks

2016 ◽  
Vol 195 ◽  
pp. 699-710 ◽  
Author(s):  
David Chandler ◽  
David E. Manolopoulos
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
Reaction Rate ◽  
Rare Event ◽  
State Theory ◽  
Rate Theory ◽  
Reaction Rate Theory ◽  
Adiabatic Dynamics

This paper summarizes the contributions to the Faraday Discussion on reaction rate theory. The topics range from contemporary usage of transition state theory, including rare event sampling, to instantons and non-adiabatic dynamics.

scholarly journals The Limitation of the Combination of Transition State Theory and Thermodynamics for the Reactions of Proteins and Nucleic Acids

Biomolecules ◽  
2021 ◽  
Vol 12 (1) ◽  
pp. 28
Author(s):  
Nobuo Shimamoto
Keyword(s):  
Nucleic Acids ◽  
Transition State ◽  
Stationary State ◽  
Transition State Theory ◽  
Reaction Rate ◽  
State Theory

When a reaction is accompanied by a change with the speed close to or slower than the reaction rate, a circulating reaction flow can exist among the reaction states in the macroscopic stationary state. If the accompanying change were at equilibrium in the timescale of the relevant reaction, the transition-state theory would hold to eliminate the flow.

Limitations of Variational Transition State Theory for Barrierless Radical–Radical Recombination Reactions

2004 ◽  
Vol 218 (4) ◽  
pp. 457-468 ◽  
Author(s):  
Jürgen Troe
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
Classical Trajectory ◽  
State Theory ◽  
Nonadiabatic Dynamics ◽  
Variational Transition State Theory ◽  
Radical Recombination ◽  
Adiabatic Dynamics ◽  
Recombination Reactions ◽  
Variational Transition State

AbstractVariational transition state theory (VTST) is widely used for the modelling of barrierless radical-radical recombination reactions. In this application, VTST suffers from a number of limitations some of which are of more technical, others of more fundamental nature. The former are caused by inappropriate averaging over individual adiabatic channel potentials or by the neglect of quantum effects, the latter are due to deviations from adiabatic dynamics. It is shown that most radical-radical recombination reactions are characterized by Massey parameters which are smaller than unity such that the dynamics is nonadiabatic. VTST treatments which generally assume adiabatic dynamics, therefore, have a fundamental problem. Calculations of rate constants by VTST often exceed classical trajectory results by about 10 to 20percent. This is normally attributed to “recrossing trajectories”. In the present work it is shown, however, that deviations of this magnitude also have to be expected for nonadiabatic dynamics in comparison to adiabatic dynamics. It is, therefore, suggested that “recrossing” at least in part has to be attributed to nonadiabatic dynamics. A way out of the dilemma is the use of a combination of statistical adiabatic channel and classical trajectory concepts.

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