The rate of methyl radical decomposition at high temperatures and pressures

Su, Joseph Zhichun; Teitelbaum, Heshel

doi:10.1002/kin.550260116

Cited by 7 publications

(5 citation statements)

References 38 publications

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“…The theoretical analysis of the experimental rate constant of channel (R2) as presented in ref. 19 is not applicable because the theoretical low-pressure limiting rate constant must represent the energetically lowest channel (R1). Due to the complication from rotational channel switching (see above) the true low-pressure limit of reaction (R1) has yet not been observed directly.…”

Section: Decomposition Ratesmentioning

confidence: 99%

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Branching ratios and incubation times in the thermal decomposition of methyl radicals: Experiments and theory

Eng

Gebert

Goos

et al. 2001

Phys. Chem. Chem. Phys.

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Section: Decomposition Ratesmentioning

confidence: 99%

“…Only the energetically less favored channel R2 has been analyzed with simpliÐed SACM theory in ref. 19. H following the reverse of reactions (R3) and (R4), respectively, or may be stabilized with sufficiently frequent collisions.…”

Section: Introductionmentioning

confidence: 99%

Branching ratios and incubation times in the thermal decomposition of methyl radicals: Experiments and theory

Eng

Gebert

Goos

et al. 2001

Phys. Chem. Chem. Phys.

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“…In our method, we do not include any adjustable parameters. Somewhat related to this study, rate constants for the decomposition of the methyl radical have been calculated by Su and Teitelbaum for the falloff curves over a wide range of temperatures.…”

Section: Introductionmentioning

confidence: 99%

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociation Reactions of Interest in Organometallic Vapor-Phase Epitaxy (OMVPE)

et al. 2003

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A procedure for calculating homolytic dissociation rate constants is reported for modeling organometallic vapor-phase epitaxy (OMVPE) of III−V compounds for all pressure regimes. Reaction rate constants were predicted following a semiclassical approach based on quantum mechanical calculations and transition-state theory. The critical configuration was determined using linear interpolations for the geometry of the intermediate structures, Morse potentials for the intermediate electronic energies, and Hase's relationship for the vibrational frequencies that become annihilated. Low-pressure rate constants were calculated from Rice−Ramsperger−Kassel−Marcus (RRKM) theory following the Troe approach. The calculations were compared with experimental values for the dissociation of one methyl radical from the closed-shell molecules Al(CH3)3, Ga(CH3)3, and In(CH3)3 and the radical molecules Ga(CH3)2 and In(CH3) and for the dissociation of one hydrogen atom from NH3, PH3, and AsH3. A simplified system of reactions for the homolytic dissociation of In(CH3)3 was modeled in an OMV reactor designed for the pressure range 10-2 to 102 atm using computational fluid dynamics coupled with chemical kinetics. The steady-state simulations were carried out at 1000 K and at N2 pressures of 1 and 20 atm.

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“…Spectroscopic and potential constants are listed in Table I 22,28–48. The H m, i – H m, j interaction in CH 3 can be estimated in terms of the Lennard–Jones parameters for CH 3 ⋅⋅⋅CH 3 , ε

_{H_{italicm}}

H m / k B = 144 K and σ

_{H_{italicm}}

H m = 3.8 Å 49, where i , j are deleted for convenience.…”

Section: Collision Model and Methodsmentioning

confidence: 99%

Dynamics of the CH₃ + OH reaction

Ree

Kim

Shin

2011

Int J of Chemical Kinetics

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We study dynamics of the CH 3 + OH reaction over the temperature range of 300-2500 K using a quasiclassical method for the potential energy composed of explicit forms of short-range and long-range interactions. The explicit potential energy used in the study gives minimum energy paths on potential energy surfaces showing barrier heights, channel energies, and van der Waals well, which are consistent with ab initio calculations. Approximately, 20% of CH 3 + OH collisions undergo OH dissociation in a direct-mode mechanism on a subpicosecond scale (<50 fs) with the rate coefficient as high as ∼10 −10 cm 3 molecule −1 s −1 . Less than 10% leads to the formation of excited intermediates CH 3 OH † with excess vibrational energies in CO and OH bonds. CH 3 OH † stabilizes to CH 3 OH, redissociates back to reactants, or forms one of various products after intramolecular energy redistribution via bond dissociation and formation on the time scale of 50-200 fs. The principal product is 1 CH 2 (k CH 2 being ∼10 −11 ), whereas ks for CH 2 OH, CH 2 O, and CH 3 O are ∼10 −12 . The minor products are HCOH and CH 4 (k ∼10 −13 ). The total rate coefficient for CH 3 + OH → CH 3 OH † → products is ∼10 −11 and is weakly dependent on temperature. C

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The rate of methyl radical decomposition at high temperatures and pressures

Cited by 7 publications

References 38 publications

Branching ratios and incubation times in the thermal decomposition of methyl radicals: Experiments and theory

Branching ratios and incubation times in the thermal decomposition of methyl radicals: Experiments and theory

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociation Reactions of Interest in Organometallic Vapor-Phase Epitaxy (OMVPE)

Dynamics of the CH₃ + OH reaction

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The rate of methyl radical decomposition at high temperatures and pressures

Cited by 7 publications

References 38 publications

Branching ratios and incubation times in the thermal decomposition of methyl radicals: Experiments and theory

Branching ratios and incubation times in the thermal decomposition of methyl radicals: Experiments and theory

Semiclassical Calculation of Reaction Rate Constants for Homolytical Dissociation Reactions of Interest in Organometallic Vapor-Phase Epitaxy (OMVPE)

Dynamics of the CH3 + OH reaction

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Dynamics of the CH₃ + OH reaction