Theory of Detonations. I. Irreversible Unimolecular Reaction

1958 ◽  
Vol 28 (6) ◽  
pp. 1130-1147 ◽  
Author(s):  
Joseph O. Hirschfelder ◽  
Charles F. Curtiss
Keyword(s):  
Unimolecular Reaction

Computational Study on the Kinetics and Mechanisms of Unimolecular Reactions of (Z)-(Z)-N-(λ5-phosphanylidene) Formohydrazonic Formic Anhydride: Intramolecular aza-Wittig Reaction in Competition with Mumm Rearrangement

2020 ◽  
Vol 17 (11) ◽  
pp. 884-889
Author(s):  
Somayeh Mirdoraghi ◽  
Hamed Douroudgari ◽  
Farideh Piri ◽  
Morteza Vahedpour
Keyword(s):  
Rate Constants ◽  
Density Functional ◽  
Wittig Reaction ◽  
Computational Study ◽  
Single Step ◽  
Low Energy ◽  
Coupled Cluster ◽  
Unimolecular Reaction ◽  
Single Step Reaction ◽  
Good Agreement

For (Z)-(Z)-N-(λ5-phosphanylidene) formohydrazonic formic anhydride, Aza-Wittig reaction and Mumm rearrangement are studied using both density functional and coupled cluster theories. For this purpose, two different products starting from one substrate are considered that are competing with each other. The obtained products, P1 and P2, are thermodynamically favorable. The product of the aza-Wittig reaction, P1, is more stable than the product of Mumm rearrangement (P2). For the mentioned products, just one reliable pathway is separately proposed based on unimolecular reaction. Therefore, the rate constants based on RRKM theory in 300-600 K temperature range are calculated. Results show that the P1 generation pathway is a suitable path due to low energy barriers than the path P2. The first path has three steps with three transition states, TS1, TS2, and TS3. The P2 production path is a single-step reaction. In CCSD level, the computed barrier energies are 14.55, 2.196, and 10.67 kcal/mol for Aza-Wittig reaction and 42.41 kcal/mol for Mumm rearrangement in comparison with the corresponding complexes or reactants. For final products, the results of the computational study are in a good agreement with experimental predictions.

Unimolecular Reaction Rate Constants of NO2Just above D0

1999 ◽  
Vol 103 (49) ◽  
pp. 10268-10273 ◽  
Author(s):  
I. Bezel ◽  
D. Stolyarov ◽  
C. Wittig
Keyword(s):  
Rate Constants ◽  
Reaction Rate ◽  
Unimolecular Reaction ◽  
Reaction Rate Constants

Predicting nonstatistical unimolecular reaction rates using Kramers’ theory

1999 ◽  
Vol 110 (12) ◽  
pp. 5514-5520 ◽  
Author(s):  
Yin Guo ◽  
Dmitrii V. Shalashilin ◽  
Justin A. Krouse ◽  
Donald L. Thompson
Keyword(s):  
Reaction Rates ◽  
Unimolecular Reaction

Interpolating moving least-squares methods for fitting potential energy surfaces: An application to the H2CN unimolecular reaction

2007 ◽  
Vol 126 (10) ◽  
pp. 104105 ◽  
Author(s):  
Yin Guo ◽  
Lawrence B. Harding ◽  
Albert F. Wagner ◽  
Michael Minkoff ◽  
Donald L. Thompson
Keyword(s):  
Potential Energy ◽  
Least Squares ◽  
Potential Energy Surfaces ◽  
Moving Least Squares ◽  
Unimolecular Reaction ◽  
Energy Surfaces
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