Mechanism of the OH–propene–O2 reaction: An ab initio study

Diaz-Acosta, Irina; Álvarez-Idaboy, J. Raúl; Vivier–Bunge, Annik

doi:10.1002/(sici)1097-4601(1999)31:1<29::aid-kin4>3.3.co;2-e

Cited by 24 publications

(40 citation statements)

References 7 publications

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“…This interaction is similar to that found in alkenes + OH reactions. 41 The high p character of the C-C bonds in cyclopropane and its tendency to show alkene-like behavior have been previously reported. 42-49 However, to the best of our knowledge, the existence of the alkene-like complexes reported in here, has not been formerly described.…”

Section: Resultscontrasting

confidence: 65%

Isopropylcyclopropane + OH Gas Phase Reaction: A Quantum Chemistry + CVT/SCT Approach

2006

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A theoretical study of the mechanism and kinetics of the OH hydrogen abstraction from isopropylcyclopropane (IPCP) is presented. Optimum geometries, frequencies and gradients have been computed at the BHandHLYP/6-311++G(d,p) level of theory for all stationary points, as well as for additional points along the minimum energy path (MEP). Energies have been improved by single-point calculations at the above geometries using CCSD(T)/6-311++G(d,p) to produce the potential energy surface. The rate coefficients are calculated for the temperature range 260-350 K by using canonical variational theory (CVT) with small-curvature tunneling (SCT) corrections. Our analysis suggests a stepwise mechanism involving the formation of a reactant complex in the entrance channel and a product complex in the exit channel, for all the modeled paths. The reactant complexes are examined in detail, because they exhibit alkene-like structure. The excellent agreement between the overall calculated and experimental rate coefficients at 298 K supports the reliability of the parameters obtained for the temperature dependence and branching ratios of the IPCP + OH reaction, proposed here for the fist time. The expression that best describes the studied reaction is k(overall) = 6.15 x 10(-13)e1747/RT cm3 x molecule(-1) x s(-1). The predicted activation energy is -0.89 kcal/mol.

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Section: Resultscontrasting

confidence: 65%

Isopropylcyclopropane + OH Gas Phase Reaction: A Quantum Chemistry + CVT/SCT Approach

2006

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“…A van der Waals complex was formed prior to addition have been reported in quantum chemical studies on the OH addition reaction to alkenes [30,32,33]. A transition state connecting the van der Waals complex with the adduct has also been found.…”

Section: Resultsmentioning

confidence: 80%

Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

Jiang

Wang

2009

IJMS

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The addition reactions of NO3 to limonene have been investigated using ab initio methods. Six different possibilities for NO3 addition to the double bonds, which correspond to the two C–C double bonds (endocyclic or exocyclic) have been considered. The negative activation energies for the addition of NO3 to limonene are calculated and the energies of NO3-limonene radical adducts are found to be 14.55 to 20.17 kcal mol-1 more stable than the separated NO3 and limonene at the CCSD(T)/6–31G(d) + CF level. The results also indicate that the endocyclic addition reaction is more energetically favorable than the exocyclic one.

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“…Specifically, the most relevant pathways reported in the literature [118][119][120][121][122][123][124] are obtained with tsscds, except for the barrierless dissociation leading to propene + OH, since the present version of tsscds cannot handle this type of reactions. Of significance, an important number of reactant and TS conformers, not described in the previous studies, are obtained with tsscds.…”

Section: Combustion Chemistrymentioning

confidence: 99%

A Trajectory-Based Method to Explore Reaction Mechanisms

Vázquez¹,

Otero²,

Martı́nez-Núñez³

2018

Preprint

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The method tsscds, recently developed in our group, discovers chemical reaction mechanisms with minimal human intervention. It employs accelerated molecular dynamics, spectral graph theory, statistical rate theory and stochastic simulations to uncover chemical reaction paths and to solve the kinetics at the experimental conditions. In the present review, its application to solve mechanistic/kinetics problems in different research areas will be presented. Examples will be given of reactions involved in photodissociation dynamics, mass spectrometry, combustion chemistry and organometallic catalysis. Some planned improvements will also be described. The source code can be downloaded from: http://forge.cesga.es/wiki/g/tsscds/HomePage

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Mechanism of the OH–propene–O2 reaction: An ab initio study

Cited by 24 publications

References 7 publications

Isopropylcyclopropane + OH Gas Phase Reaction: A Quantum Chemistry + CVT/SCT Approach

Isopropylcyclopropane + OH Gas Phase Reaction: A Quantum Chemistry + CVT/SCT Approach

Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

A Trajectory-Based Method to Explore Reaction Mechanisms

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