Effect of fluctuations in state-specific unimolecular rate constants on the pressure dependence of the average unimolecular reaction rate

1988 ◽  
Vol 92 (15) ◽  
pp. 4261-4263 ◽  
Author(s):  
William H. Miller
Keyword(s):  
Pressure Dependence ◽  
Rate Constants ◽  
Reaction Rate ◽  
Unimolecular Reaction

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

The Low-Energy Unimolecular Reaction Rate Constants for the Gas Phase, Ni+-Mediated Dissociation of the C−C σ Bond in Acetone

2009 ◽  
Vol 113 (39) ◽  
pp. 10417-10424 ◽  
Author(s):  
Vanessa A. Castleberry ◽  
S. Jason Dee ◽  
Otsmar J. Villarroel ◽  
Ivanna E. Laboren ◽  
Sarah E. Frey ◽  
...  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Reaction Rate ◽  
Low Energy ◽  
Unimolecular Reaction ◽  
Reaction Rate Constants

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.

Measurement of the OH Reaction Rate Constants for CF3CH2OH, CF3CF2CH2OH, and CF3CH(OH)CF3

1999 ◽  
Vol 103 (15) ◽  
pp. 2664-2672 ◽  
Author(s):  
Kazuaki Tokuhashi ◽  
Hidekazu Nagai ◽  
Akifumi Takahashi ◽  
Masahiro Kaise ◽  
Shigeo Kondo ◽  
...  
Keyword(s):  
Rate Constants ◽  
Reaction Rate ◽  
Reaction Rate Constants

scholarly journals PREDICTION OF REACTION RATE CONSTANTS OF HYDROXYL RADICAL WITH ORGANIC COMPOUNDS

2014 ◽  
Vol 59 (1) ◽  
pp. 2252-2259 ◽  
Author(s):  
ZHEN CHEN ◽  
XINLIANG YU ◽  
XIANWEI HUANG ◽  
SHIHUA ZHANG
Keyword(s):  
Hydroxyl Radical ◽  
Organic Compounds ◽  
Rate Constants ◽  
Reaction Rate ◽  
Reaction Rate Constants
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