scholarly journals Multi-path variational transition state theory for chiral molecules: the site-dependent kinetics for abstraction of hydrogen from 2-butanol by hydroperoxyl radical, analysis of hydrogen bonding in the transition state, and dramatic temperature dependence of the activation energy

2015 ◽  
Vol 6 (10) ◽  
pp. 5866-5881 ◽  
Author(s):  
Junwei Lucas Bao ◽  
Rubén Meana-Pañeda ◽  
Donald G. Truhlar
Keyword(s):  
Activation Energy ◽  
Hydrogen Bond ◽  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Chiral Molecules ◽  
Hydroperoxyl Radical ◽  
Variational Transition State Theory ◽  
Free Energy Of Activation ◽  
Enthalpy Of Activation

A hydrogen bond at the transition state can lower the enthalpy of activation, but raise the free energy of activation.

Understanding the activation energy trends for the C2H4+OH→C2H4OH reaction by using canonical variational transition state theory

1997 ◽  
Vol 107 (18) ◽  
pp. 7266-7274 ◽  
Author(s):  
Jordi Villà ◽  
Angels González-Lafont ◽  
José M. Lluch ◽  
José C. Corchado ◽  
Joaquı́n Espinosa-Garcı́a
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Transition State Theory ◽  
State Theory ◽  
Variational Transition State Theory ◽  
Variational Transition State

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.

scholarly journals Kinetic Analysis of the Effect of Poliovirus Receptor on Viral Uncoating: the Receptor as a Catalyst

2001 ◽  
Vol 75 (11) ◽  
pp. 4984-4989 ◽  
Author(s):  
Simon K. Tsang ◽  
Brian M. McDermott ◽  
Vincent R. Racaniello ◽  
James M. Hogle
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Kinetic Analysis ◽  
Transition State Theory ◽  
State Theory ◽  
Viral Receptor ◽  
Poliovirus Receptor ◽  
Entropic Stabilization ◽  
Entropic Effects

ABSTRACT We examined the role of soluble poliovirus receptor on the transition of native poliovirus (160S or N particle) to an infectious intermediate (135S or A particle). The viral receptor behaves as a classic transition state theory catalyst, facilitating the N-to-A conversion by lowering the activation energy for the process by 50 kcal/mol. In contrast to earlier studies which demonstrated that capsid-binding drugs inhibit thermally mediated N-to-A conversion through entropic stabilization alone, capsid-binding drugs are shown to inhibit receptor-mediated N-to-A conversion through a combination of enthalpic and entropic effects.

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