Mechanism of the OH-propene-O2 reaction: Anabinitio study

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

doi:10.1002/(sici)1097-4601(1999)31:1<29::aid-kin4>3.0.co;2-n

Cited by 50 publications

(47 citation statements)

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“…Several detailed theoretical studies [4][5][6][20][21][22][23][24] have been carried out for the energetics of propene and OH reaction. In a recent paper, Za ´dor et al 5 employed RQCISD(T)/ccpVpZ//B3LYP/ 6-311++G(d,p) quantum chemical calculations combined with RRKM Master Equation (ME) methodology to investigate the branching ratios for various channels that are accessible on the C 3 H 7 O potential energy surface.…”

Section: Introductionmentioning

confidence: 99%

A shock tube study of the branching ratios of propene + OH reaction

Badra

Khaled

Giri

et al. 2015

Phys. Chem. Chem. Phys.

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CitationA shock tube study of the branching ratios of propene + OH reaction 2015, 17 (4) pressures near 1 atm. The reaction progress was followed by monitoring OH radical near 306.7 nm using UV laser absorption. Kinetic isotope effects in the measured rate coefficients are discussed and rationalized for the site-specific H abstraction by OH radical. The first experimental measurements for the branching ratio of the title reaction are reported and compared with transition state theory calculations. The allylic H-atom abstraction of propene by OH radicals was found to be the most dominant reaction pathway followed by propen-1-yl and propen-2-yl channels over the entire temperature range of this study. The derived Arrhenius expressions for various site-specific rate coefficients over 818 -1442 K are (the subscript in the rate coefficient identifies the position of H or D atom according to the IUPAC nomenclature of alkenes):

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Section: Introductionmentioning

confidence: 99%

A shock tube study of the branching ratios of propene + OH reaction

Badra

Khaled

Giri

et al. 2015

Phys. Chem. Chem. Phys.

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“…Indeed, it has been generally assumed that, because the experimental activation energy of the reaction is negative, the barrier for the formation of the adducts should be negligible in all cases. In light of our previous experience with OH addition to double bonds in the case of ethene and propene 20 and of substituted ethenes, 21 we believe that sizable barriers may exist. In this work, this assumption has been tested by means of accurate molecular orbital calculations of the stationary points along the four possible addition pathways.…”

Section: Introductionmentioning

confidence: 88%

Theoretical study of the initial reaction between OH and isoprene in tropospheric conditions

Francisco‐Márquez

Álvarez-Idaboy

Galano

et al. 2003

Phys. Chem. Chem. Phys.

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The reaction of isoprene with OH radicals has been investigated by ab initio molecular orbital theory. We report the energetics of four different pathways, involving the direct addition of OH to four of the carbon atoms. Calculations have been performed using both density functional theory (BHandHLYP) and Møller-Plesset perturbation theory to the second-order (MP2). Two pre-reactive complexes have been identified, whose stabilization energy with respect to the separated reactants is about 12 kJ mol À1 . Their structure is similar to the ones previously reported for OH-ethene and OH-propene adducts: the OH radical is placed over either one of the double bonds at a distance of about 2.1 A ˚, with the H atom pointing towards the C-C bond. The geometries of the transition states corresponding to OH addition at the four different positions have been optimized. The calculated apparent activation energies are negative for addition at the terminal carbon atoms and in excellent agreement with the experimental measurements. Direct addition at the internal carbon atoms involves much higher energy barriers, and these pathways are expected to be negligible at normal temperatures. Thus, the observed formation of 3-methylfuran must occur after radical addition to the terminal carbon atoms, following a pathway such as the one proposed by R.

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“…17 kJ mol À1 for OH + propene. 41 Ultimately, for reactions in a homologous series, we wish to estimate what combination of parameters will cause the energy of the inner barrier to be zero. If we set a critical barrier energy (E b ) of zero, we can solve eqn (E5) to give the value of (I.E.…”

Section: Temperature-dependence Of Rapid Low Temperature Reactionsmentioning

confidence: 99%

The temperature-dependence of rapid low temperature reactions: experiment, understanding and prediction

Smith¹,

et al. 2006

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Despite the success of the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme) method in measuring rate coefficients for neutral-neutral reactions of radicals down close to the very low temperatures prevalent in dense interstellar clouds (ISCs), there are still many reactions of potential importance in the chemistry of these objects for which there have been no measurements of low temperature rate coefficients. One important class of reactions is that between atomic and molecular free radicals and unsaturated hydrocarbons; that is, alkynes and alkenes. Based on semi-empirical arguments and correlations of 'room temperature' rate coefficients, k(298 K), for reactions of this type with the difference between the ionisation energy of the alkyne/alkene and the electron affinity of the radical, we suggest which reactions between the radicals, C(3P), O(3P), N(4S), CH, C2H and CN, and carbon chain molecules (Cn) and cyanopolyynes (HC2nCN and NCC2nCN) are likely to be fast at the temperature of dense ISCs. These reactions and rate coefficients have been incorporated into a purely gas-phase model (osu2005) of ISC chemistry. The results of these calculations are presented and discussed.

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Mechanism of the OH-propene-O2 reaction: Anabinitio study

Cited by 50 publications

References 13 publications

A shock tube study of the branching ratios of propene + OH reaction

A shock tube study of the branching ratios of propene + OH reaction

Theoretical study of the initial reaction between OH and isoprene in tropospheric conditions

The temperature-dependence of rapid low temperature reactions: experiment, understanding and prediction

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