On nascent angular‐momentum distributions in complex‐forming bimolecular reactions

Olzmann, Matthias

doi:10.1002/bbpc.19971010328

Cited by 15 publications

(3 citation statements)

References 32 publications

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“…From their experiments DeMore and Lin suggested 0.8 ps [25] while van Zee and Stevenson [26] derived about 3 ps. Statistical theories (SACM) predict a lifetime close to 10 ps [27].…”

Section: Discussionmentioning

confidence: 98%

“…(8) In this equation Φ 0 is the OH-yield in the low pressure limit which was assumed to be 0.71. k(E ac ) is the specific rate constant for reaction (2a) at the excitation energy E ac and was set to be 1ϫ10 11 s Ϫ1 as calculated by SACM [27]. Z LJ is the Lennard-Jones collision number and was calculated to be 3.9ϫ10 Ϫ10 cm 3 s Ϫ1 according to the parameters given in ref.…”

Section: Discussionmentioning

confidence: 99%

“…The appearance of OH-radicals was monitored by subpicosecond LIF and from the rise of the OH-LIF-signal a lifetime of about 3 ps was obtained for the chemically activated methanol. A statistical adiabatic channel model (SACM) calculation was performed by Olzmann [27] and a lifetime of about 10 ps was obtained for chemically activated methanol from thermal O( 1 D)-atoms reacting with CH 4 at room temperature. The agreement between these two values is fairly good considering the translationally hot O( 1 D)-atoms in the cluster photolysis experiments.…”

Section: Introductionmentioning

confidence: 99%

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The OH-yield in the reaction of O(1D) + CH4 under high pressure conditions up to 560 bar helium

Ausfelder¹,

Hippler²,

Striebel³

2000

Zeitschrift Für Physikalische Chemie

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The pressure dependence of the OH yield in the reaction O( 1 D) ϩ CH 4 has been investigated at room temperature in the pressure range from 4 to 560 bar of helium. O( 1 D)-atoms were generated by pulsed laser photolysis (PLP) of N2O and OH-radicals were detected by saturated laser induced fluorescence (SLIF). The OH-yield was determined relative to the OH yield in the reaction of O( 1 D) with H2 which is assumed to be unity and pressure independent. Within the pressure range of our experiments we found a constant OH-yield of (71Ϯ 5) % in the reaction of O( 1 D) with methane. From the OH fluorescence lifetime at the highest pressures near 500 bar of helium we obtained the rate constant for the collisional deactivation of electronically OH radicals of kq(He) ϭ (3 Ϯ0.3) ϫ10 Ϫ15 cm 3 s Ϫ1 , corresponding to a cross section of σq(He) ϭ (2.1 Ϯ 0.2)ϫ 10 Ϫ20 cm 2 . The rate constant for collisional deactivation of vibrationally excited OH radicals in the electronic ground state OH(v ϭ 1) ϩ He → OH(vϭ 0) ϩ He (reaction (5)) was determined to be k5(He) ϭ (1.2 Ϯ 0.2)ϫ 10 Ϫ16 cm 3 s Ϫ1 .

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“…From their experiments DeMore and Lin suggested 0.8 ps [25] while van Zee and Stevenson [26] derived about 3 ps. Statistical theories (SACM) predict a lifetime close to 10 ps [27].…”

Section: Discussionmentioning

confidence: 98%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The OH-yield in the reaction of O(1D) + CH4 under high pressure conditions up to 560 bar helium

Ausfelder¹,

Hippler²,

Striebel³

2000

Zeitschrift Für Physikalische Chemie

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The gas phase reactions of benzyl radicals with O, O₃, and NO₃: Rate, mechanism, and unimolecular decomposition of the chemically activated benzoxy radical

Hoyermann

Seeba

Olzmann

et al. 1997

Ber Bunsenges Phys Chem

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The reactions of the benzyl radical with O, O3, and NO3 are investigated in a discharge flow‐reactor with mass spectrometric detection. For the rate coefficients of the latter two reactions, we obtain values of 2.8·1013 and 1.93·1012 cm3 mol−1s−1, respectively (T≈300 K, P ≈ 2 mbar). The main products for all three reactions are C6H6 and C6H5CHO with relative yields of 0.60/0.40 (M. Bartels, J. Edelbüttel‐Einhaus, and K. Hoyermann, 22nd Int. Symp. on Combustion, p. 1041, The Combustion Institute. Pittsburgh 1988), 0.37/0.66, and 0.23/0.77, respectively. These branching fractions are interpreted in terms of the unimolecular decomposition of an intermediarily formed benzoxy radical, using statistical rate theory. The molecular data needed are calculated by quantum chemical methods. The verification of the experimental branching fractions requires the assumption of a direct reaction channel leading from C6H5CH2O to C6H6. The nature of this channel is still uncertain.

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Kinetics of the reactions of HCO with H and D atoms

Ziemer¹,

Dóbé²,

Wagner³

et al. 1998

Ber Bunsenges Phys Chem

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The rate constants for the reactions HCO+H → products (1) and HCO+D → products (2) were determined at room temperature in an isothermal discharge flow reactor. Atom and radical concentrations in the reactions were monitored using Electron Paramagnetic Resonance (EPR) for H and D atoms and Far Infrared Laser Magnetic Resonance (FIR‐LMR) and Laser Induced Fluorescence (LIF) for HCO. The overall rate constants describing the decay of the HCO concentrations with H and D, respectively, were found to be k1=(6.8±2.0)×1013 cm3 mol−1 s−1 and k2=(8.3±2.5)×1013 cm3 mol−1 s−1. The results are discussed assuming a mechanism that allows for parallel reaction pathways via a direct H atom abstraction reaction or via an addition‐elimination reaction through a short‐lived highly vibrationally excited formaldehyde complex.

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On nascent angular‐momentum distributions in complex‐forming bimolecular reactions

Cited by 15 publications

References 32 publications

The OH-yield in the reaction of O(1D) + CH4 under high pressure conditions up to 560 bar helium

The OH-yield in the reaction of O(1D) + CH4 under high pressure conditions up to 560 bar helium

The gas phase reactions of benzyl radicals with O, O₃, and NO₃: Rate, mechanism, and unimolecular decomposition of the chemically activated benzoxy radical

Kinetics of the reactions of HCO with H and D atoms

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On nascent angular‐momentum distributions in complex‐forming bimolecular reactions

Cited by 15 publications

References 32 publications

The OH-yield in the reaction of O(1D) + CH4 under high pressure conditions up to 560 bar helium

The OH-yield in the reaction of O(1D) + CH4 under high pressure conditions up to 560 bar helium

The gas phase reactions of benzyl radicals with O, O3, and NO3: Rate, mechanism, and unimolecular decomposition of the chemically activated benzoxy radical

Kinetics of the reactions of HCO with H and D atoms

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The gas phase reactions of benzyl radicals with O, O₃, and NO₃: Rate, mechanism, and unimolecular decomposition of the chemically activated benzoxy radical