Dynamical corrections to transition state theory for multistate systems: Surface self‐diffusion in the rare‐event regime

1985 ◽  
Vol 82 (1) ◽  
pp. 80-92 ◽  
Author(s):  
Arthur F. Voter ◽  
Jimmie D. Doll
Keyword(s):  
Transition State ◽  
Transition State Theory ◽  
Rare Event ◽  
State Theory ◽  
Self Diffusion ◽  
Multistate Systems

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.

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.

Microscopic Interpretation of Arrhenius Parameters

2018 ◽  
Author(s):  
Niels Engholm Henriksen ◽  
Flemming Yssing Hansen
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Transition State Theory ◽  
Average Energy ◽  
Zero Point ◽  
State Theory ◽  
Exponential Factor ◽  
Quantum Tunnelling ◽  
Microscopic Interpretation ◽  
The Difference

This chapter reviews the microscopic interpretation of the pre-exponential factor and the activation energy in rate constant expressions of the Arrhenius form. The pre-exponential factor of apparent unimolecular reactions is, roughly, expected to be of the order of a vibrational frequency, whereas the pre-exponential factor of bimolecular reactions, roughly, is related to the number of collisions per unit time and per unit volume. The activation energy of an elementary reaction can be interpreted as the average energy of the molecules that react minus the average energy of the reactants. Specializing to conventional transition-state theory, the activation energy is related to the classical barrier height of the potential energy surface plus the difference in zero-point energies and average internal energies between the activated complex and the reactants. When quantum tunnelling is included in transition-state theory, the activation energy is reduced, compared to the interpretation given in conventional transition-state theory.

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