Dynamics of CO formation in the reaction O(3P)+C2H3

Donaldson, D. J.; Okuda, I.; Sloan, J. J.

doi:10.1016/0301-0104(94)00407-2

Cited by 39 publications

(30 citation statements)

References 26 publications

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“…NO 2 was expanded through a 1.0 mm-diameter pulsed valve and a 40.0 mm-long piezoelectric nozzle, and irradiated with the 355 nm output of a Nd:YAG laser (6.0 mm diameter, 30 mJ/pulse, Continuum Surelite II-10) near the throat of the supersonic expansion. The second pulsed beam of (CH 3 ) 2 CH radicals was produced by supersonic flash pyrolysis of isopropyl bromide, (CH 3 ) 2 CHBr, which has a weak CÀBr bond (BDE = 71.5 kcal mol À1 ). The precursor, seeded in 2 atm UHP He, underwent quantitative thermal decomposition into (CH 3 ) 2 CH and atomic bromine (Br) inside a hot SiC tube and was then expanded supersonically into the scattering chamber.…”

Section: Methodsmentioning

confidence: 99%

“…The corresponding activation barriers were calculated to be 13.6 and 17.6 kcal mol À1 , respectively. Considering the reaction barrier heights, exothermicities and numbers of intermediates, the most facile addition pathway was predicted to be reaction channel (2) leading to the formation of acetaldehyde and CH 3 . Figure 4 at the CBS-QB3 level of theory.…”

Section: Ab Initio Reaction Pathways: Addition Versus Abstractionmentioning

confidence: 99%

“…In previous reactive scattering experiments using FTIR spectroscopy Donalson et al and Leone et al independently studied exoergic reactions of O( 3 P) with several alkyl radicals and observed strongly nonstatistical internal energy distributions of diatomic products. [2,3] Leonori et al also studied the oxidation of allyl radicals using crossed beams. [4] This work reports a combined crossed-beam and ab initio study of the gas-phase oxidation dynamics of isopropyl radicals, (CH 3 ) 2 CH.…”

Section: Introductionmentioning

confidence: 99%

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Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

2012

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This paper reports on the gas-phase radical-radical dynamics of the reaction of ground-state atomic oxygen [O((3)P), from the photodissociation of NO(2)] with secondary isopropyl radicals [(CH(3))(2)CH, from the supersonic flash pyrolysis of isopropyl bromide]. The major reaction channel, O((3)P)+(CH(3))(2)CH→C(3)H(6) (propene)+OH, is examined by high-resolution laser-induced fluorescence spectroscopy in crossed-beam configuration. Population analysis shows bimodal nascent rotational distributions of OH (X(2)Π) products with low- and high-N'' components in a ratio of 1.25:1. No significant spin-orbit or Λ-doublet propensities are exhibited in the ground vibrational state. Ab initio computations at the CBS-QB3 theory level and comparison with prior theory show that the statistical method is not suitable for describing the main reaction channel at the molecular level. Two competing mechanisms are predicted to exist on the lowest doublet potential-energy surface: direct abstraction, giving the dominant low-N'' components, and formation of short-lived addition complexes that result in hot rotational distributions, giving the high-N'' components. The observed competing mechanisms contrast with previous bulk kinetic experiments conducted in a fast-flow system with photoionization mass spectrometry, which suggested a single abstraction pathway. In addition, comparison of the reactions of O((3)P) with primary and tertiary hydrocarbon radicals allows molecular-level discussion of the reactivity and mechanism of the title reaction.

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Section: Methodsmentioning

confidence: 99%

Section: Ab Initio Reaction Pathways: Addition Versus Abstractionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

2012

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“…3 For bimolecular reactive scattering processes, only a few experimental studies have been reported in recent years. The exoergic reaction of ground-state atomic oxygen [O( 3 P 2 )] with vinyl radicals (C 2 H 3 ) using arrested relaxation Fourier transform infrared (FT-IR) spectroscopy and non-statistical vibrational distribution of the CO product was studied by Donaldson et al 4 . The reaction of O( 3 P 2 ) with methyl radicals (CH 3 ) under low pressure flow conditions, manifesting an indirect addition mechanism was carried out by Bersohn and co-workers.…”

Section: Introductionmentioning

confidence: 99%

Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

Gupta¹,

Singh²,

Singh³

et al. 2007

J Chem Sci

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The reaction of ground-state atomic oxygen [O( 3 P 2 )] with methyl, ethyl, n-propyl and isopropyl radicals has been studied using the density functional method and the complete basis set model. The energies of the reactants, products, reaction intermediates and various transition states as well as the reaction enthalpies have been computed. The possible product channels and the reaction pathways are identified in each case. In the case of methyl radical the minimum energy reaction pathway leads to the products CO + H 2 + H. In the case of ethyl radical the most facile pathway leads to the products, methanal + CH 3 radical. For propyl radical (n-and iso-), the minimum energy reaction pathway would lead to the channel containing ethanal + methyl radical.

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“…It is of interest to note that at the MCSCF level these energies are slightly reversed 6. Note also that the acetyl radical tends to dissociate into CO and CH 3 8, thus preventing any autoionization even if the energetics allowed it. A recent G2 calculation of acetyl 9 has given a VIE of 8.39 eV, which is close to the experimental value, and an AIE of 6.66 eV.…”

Section: Resultsmentioning

confidence: 99%

Generation of the C₂H₃O⁺ ion in reactions of O(³P) with 2‐butyne

Metropoulos

2005

Int J of Quantum Chemistry

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ABSTRACT:We investigated the feasibility of formation of the C 2 H 3 O ϩ chemiion during collisions of O( 3 P) with the CH 3 C (ã 4 A 2 ), CH 2 CH (ã 4 AЉ), CH 3 C (X 2 AЉ), and CH 2 CH (X 2 AЈ) radicals, which are possible intermediates in the oxidation of 2-butyne. We determined the C-O bond dissociation energies and the ionization energies of the neutral C 2 H 3 O species as well as the C-O bond dissociation energies of C 2 H 3 O ϩ . We conclude that the CH 3 C (ã 4 A 2 ) radical is the most probable precursor of the chemiion, in agreement with experimental evidence.

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Dynamics of CO formation in the reaction O(3P)+C2H3

Cited by 39 publications

References 26 publications

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

Generation of the C₂H₃O⁺ ion in reactions of O(³P) with 2‐butyne

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Dynamics of CO formation in the reaction O(3P)+C2H3

Cited by 39 publications

References 26 publications

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(3P)+(CH3)2CH→C3H6+OH

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(3P)+(CH3)2CH→C3H6+OH

Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

Generation of the C2H3O+ ion in reactions of O(3P) with 2‐butyne

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Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

Analysis of Nascent Rotational Energy Distributions and Reaction Mechanisms of the Gas‐Phase Radical–Radical Reaction O(³P)+(CH₃)₂CH→C₃H₆+OH

Generation of the C₂H₃O⁺ ion in reactions of O(³P) with 2‐butyne