Dynamical resonances in chemical reactions

2018 ◽  
Vol 47 (17) ◽  
pp. 6744-6763 ◽  
Author(s):  
Tao Wang ◽  
Tiangang Yang ◽  
Chunlei Xiao ◽  
Zhigang Sun ◽  
Donghui Zhang ◽  
...  
Keyword(s):  
Transition State ◽  
Chemical Kinetics ◽  
Chemical Reactions ◽  
Reaction Dynamics

The transition state is a key concept in the field of chemistry and is important in the study of chemical kinetics and reaction dynamics.

scholarly journals On the theory of time dilation in chemical kinetics

2017 ◽  
Vol 31 (26) ◽  
pp. 1750177
Author(s):  
Mirza Wasif Baig
Keyword(s):  
Transition State ◽  
Chemical Kinetics ◽  
Chemical Reactions ◽  
Lorentz Transformation ◽  
Half Life ◽  
Special Theory ◽  
Time Dilation ◽  
Theory Of Relativity ◽  
Special Theory Of Relativity ◽  
Methylamine Dehydrogenase

The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying basic theories of chemical kinetics, which are transition state theory, collision theory, RRKM and Marcus theory, with the special theory of relativity. Boltzmann constant and energy spacing between permitted quantum levels of molecules are quantum mechanically proved to be Lorentz variant. The relativistic statistical thermodynamics has been developed to explain quasi-equilibrium existing between reactants and activated complex. The newly formulated Lorentz transformation of the rate constant from Arrhenius equation, of the collision frequency and of the Eyring and Marcus equations renders the rate of reaction to be Lorentz variant. For a moving observer moving at fractions of the speed of light along the reaction coordinate, the transition state possess less kinetic energy to sweep translation over it. This results in the slower transformation of reactants into products and in a stretched time frame for the chemical reaction to complete. Lorentz transformation of the half-life equation explains time dilation of the half-life period of chemical reactions and proves special theory of relativity and presents theory in accord with each other. To demonstrate the effectiveness of the present theory, the enzymatic reaction of methylamine dehydrogenase and radioactive disintegration of Astatine into Bismuth are considered as numerical examples.

On the Calculation of Transition State Activity Coefficient and Solvent Effects on Chemical Reactions

1998 ◽  
Vol 63 (12) ◽  
pp. 1969-1976 ◽  
Author(s):  
Alvaro Domínguez ◽  
Rafael Jimenez ◽  
Pilar López-Cornejo ◽  
Pilar Pérez ◽  
Francisco Sánchez
Keyword(s):  
Activity Coefficient ◽  
Transition State ◽  
Chemical Reactions ◽  
Solvent Effects ◽  
Transition State Theory ◽  
Reaction Medium ◽  
State Theory ◽  
Precursor Complex ◽  
State Activity ◽  
Classical Transition

Solvent effects, when the classical transition state theory (TST) holds, can be interpreted following the Brønsted equation. However, when calculating the activity coefficient of the transition state, γ# it is important to take into account that this coefficient is different from that of the precursor complex, γPC. The activity coefficient of the latter is, in fact, that calculated in classical treatments of salt and solvent effects. In this paper it is shown how the quotients γ#/γPC change when the reaction medium changes. Therefore, the conclusions taken on the basis of classical treatments may be erroneous.

Understanding mode-specific dynamics in the local mode representation

2018 ◽  
Vol 20 (29) ◽  
pp. 19647-19655 ◽  
Author(s):  
Hongwei Song ◽  
Minghui Yang
Keyword(s):  
Chemical Reactions ◽  
Reaction Dynamics ◽  
Local Mode ◽  
New Perspective ◽  
Elementary Chemical

Local mode representation provides a new perspective to understand reaction dynamics of elementary chemical reactions.

scholarly journals Resonant catalysis of thermally activated chemical reactions with vibrational polaritons

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Jorge A. Campos-Gonzalez-Angulo ◽  
Raphael F. Ribeiro ◽  
Joel Yuen-Zhou
Keyword(s):  
Electron Transfer ◽  
Chemical Kinetics ◽  
Chemical Reactions ◽  
Cavity Mode ◽  
Resonant Cavity ◽  
Quantum States ◽  
Transfer Model ◽  
Dark State ◽  
Thermally Activated ◽  
Two Hybrid

Abstract Interaction between light and matter results in new quantum states whose energetics can modify chemical kinetics. In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number $$N$$ N of molecular transitions couple to each resonant cavity mode, yielding two hybrid light–matter (polariton) modes and a reservoir of $$N-1$$ N − 1 dark states whose chemical dynamics are essentially those of the bare molecules. This fact is seemingly in opposition to the recently reported modification of thermally activated ground electronic state reactions under VSC. Here we provide a VSC Marcus–Levich–Jortner electron transfer model that potentially addresses this paradox: although entropy favors the transit through dark-state channels, the chemical kinetics can be dictated by a few polaritonic channels with smaller activation energies. The effects of catalytic VSC are maximal at light–matter resonance, in agreement with experimental observations.

Notiz: The Trouton-Hildebrand-Everett Rule

1998 ◽  
Vol 53 (3-4) ◽  
pp. 178 ◽  
Author(s):  
S. R. Logan
Keyword(s):  
Transition State ◽  
Chemical Kinetics ◽  
Transition State Theory ◽  
State Theory

Abstract Fundamental scientific reasons are advanced for preferring the formulation of the THE Rule offered in a Note of 1996 to that employed by Rooney in a Note of 1997. These illustrate that, whereas Transition State theory has been of considerable service to the development of chemical kinetics, it has not been of any utility in regard to issues of thermodynamics

scholarly journals Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”

2015 ◽  
Vol 80 (23) ◽  
pp. 11773-11778 ◽  
Author(s):  
Junpeng Wang ◽  
Mitchell T. Ong ◽  
Tatiana B. Kouznetsova ◽  
Jeremy M. Lenhardt ◽  
Todd J. Martínez ◽  
...  
Keyword(s):  
Transition State ◽  
Reaction Dynamics ◽  
Orbital Symmetry ◽  
Catch And Release
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