Transition state theory description of surface self‐diffusion: Comparison with classical trajectory results

1984 ◽  
Vol 80 (11) ◽  
pp. 5832-5838 ◽  
Author(s):  
Arthur F. Voter ◽  
Jimmie D. Doll
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
Classical Trajectory ◽  
State Theory ◽  
Self Diffusion

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.

scholarly journals Ion hydration: linking self-diffusion and reorientational motion to water structure

2018 ◽  
Vol 20 (8) ◽  
pp. 5909-5917 ◽  
Author(s):  
Seishi Shimizu ◽  
Nobuyuki Matubayasi
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
Water Structure ◽  
State Theory ◽  
Water Dynamics ◽  
Ion Hydration ◽  
Reorientational Motion ◽  
Self Diffusion ◽  
Jump Model ◽  
Model Transition

A link between water dynamics and the “water structure” has been established through the combination of the extended jump model, transition state theory and the Kirkwood-Buff theory.

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