Reactivity induced by complex formation: The reaction of O(3<i>P</i>) with HCl dimers

Hurwitz, Y.; Stern, Peter; Naaman, Ron; McCoy, Anne B.

doi:10.1063/1.473411

Cited by 21 publications

(10 citation statements)

References 45 publications

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“…Van Doren et al specifically observed the reaction of ion-associated HCl with chlorine nitrate Also noteworthy is the reactivity of HCl dimer, over HCl monomer, reported for reaction with atomic oxygen . A charge distribution effect is cited for 3 orders of magnitude rate enhancement.…”

Section: Discussionmentioning

confidence: 99%

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Molecular Activation by Surface Coordination: New Model for HCl Reactivity on Water−Ice Polar Stratospheric Clouds

et al. 1999

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Results of studies of the uptake of HCl by the deuterated analogue of protonated water clusters are reported. The successive uptake of nHCl n = 1−4 is observed, n = 2−4 appearing in a stepwise manner with a ratio of 6:1 D2O/HCl for the bimolecular reaction products. This primary uptake scheme is observed over a range of pressures (0.24−0.46 Torr) and temperatures (130−170 K). However, for increased flows of HCl, enhanced uptake is observed at a lower ratio of D2O/HCl, a trend that is effected by an increased buffer gas pressure. Two distinctly dominant mechanisms of HCl uptake are operative: the bimolecular uptake of HCl in a 6:1 ratio with water and a subsequent association mechanism of HCl binding to water in a 3:1 ratio. The atmospheric implications are discussed along with a proposed molecular activation by surface coordination (MASC) model for HCl uptake and subsequent reactivity on polar stratospheric clouds.

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Section: Discussionmentioning

confidence: 99%

“…46 Also noteworthy is the reactivity of HCl dimer, over HCl monomer, reported for reaction with atomic oxygen. 47 A charge distribution effect is cited for 3 orders of magnitude rate enhancement.…”

Section: Discussionmentioning

confidence: 99%

Molecular Activation by Surface Coordination: New Model for HCl Reactivity on Water−Ice Polar Stratospheric Clouds

et al. 1999

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“…28 The minor interfering background signal resulting from the photolysis of the HONO impurity that was always present in the NO 2 sample beam was subtracted to obtain the OH signal due solely to the title reaction. [29][30][31]…”

Section: Methodsmentioning

confidence: 99%

A combined crossed-beam and ab initio study of the atom–radical reaction dynamics of O(3P) + C2H5→ C2H4 + OH: analysis of nascent internal state distributions of the OH product

Park

Kang

Jung

et al. 2010

Phys. Chem. Chem. Phys.

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The oxidation reaction dynamics of ethyl radicals (C(2)H(5)) in the gas phase are investigated by applying a combination of high-resolution laser induced fluorescence spectroscopy in a crossed-beam configuration and ab initio theoretical calculations. The supersonic atomic oxygen (O((3)P)) and ethyl (C(2)H(5)) reactants are produced by photodissociation of NO(2) and supersonic flash pyrolysis of a synthesized precursor (azoethane), respectively. An exothermic channel leading to the C(2)H(5) + OH (X(2)Pi: upsilon'' = 0, 1) products is identified. The nascent rovibrational state distributions of the OH product show substantial bimodal internal excitations consisting of low- and high-N'' components with neither spin-orbit nor Lambda-doublet propensities in the ground and first excited vibrational states. The averaged vibrational population (P(upsilon'')), partitioning with respect to the low-N'' components of the upsilon'' = 0 level, shows a comparable population ratio of P(0)ratioP(1) = 1 ratio 1.06. On the basis of comparison between the population analyses using ab initio and prior statistical calculations, the title atom-radical reactive scattering processes are governed by dynamic characteristics. The reaction mechanism can be rationalized by two competing mechanisms: abstraction versus addition. The major low N''-components can be described in terms of the direct abstraction process responsible for the comparable vibrational populations, while the minor but hot rotational distribution of the high N''-components implies that some fraction of radical reactants is sampled to proceed through the short-lived addition-complex forming process.

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“…[22][23][24][25] Interfering OH background signals were excluded. First, because HONO impurity is always present in the NO 2 , the OH background resulting from NO 2 photolysis was subtracted; [26][27][28] second, background OH signal may also have arisen from the small amount of HBr impurity produced during precursor pyrolysis. However, the OH signals from the exothermic reaction O( 3 P) + HBr!OH + Br have only been reported in vibrationally excited states (u'' = 1, 2 at a ratio of 9:1) and not the u'' = 0 state.…”

Section: Nascent Rotational Distributionmentioning

confidence: 99%

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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Reactivity induced by complex formation: The reaction of O(3P) with HCl dimers

Cited by 21 publications

References 45 publications

Molecular Activation by Surface Coordination: New Model for HCl Reactivity on Water−Ice Polar Stratospheric Clouds

Molecular Activation by Surface Coordination: New Model for HCl Reactivity on Water−Ice Polar Stratospheric Clouds

A combined crossed-beam and ab initio study of the atom–radical reaction dynamics of O(3P) + C2H5→ C2H4 + OH: analysis of nascent internal state distributions of the OH product

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

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Reactivity induced by complex formation: The reaction of O(3P) with HCl dimers

Cited by 21 publications

References 45 publications

Molecular Activation by Surface Coordination: New Model for HCl Reactivity on Water−Ice Polar Stratospheric Clouds

Molecular Activation by Surface Coordination: New Model for HCl Reactivity on Water−Ice Polar Stratospheric Clouds

A combined crossed-beam and ab initio study of the atom–radical reaction dynamics of O(3P) + C2H5→ C2H4 + OH: analysis of nascent internal state distributions of the OH product

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

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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