Quantifying the non-RRKM effect in the H + O2 ? OH + O reaction

Miller, James A.; Garrett, Bruce C.

doi:10.1002/(sici)1097-4601(1997)29:4<275::aid-kin6>3.0.co;2-r

Cited by 64 publications

(56 citation statements)

References 59 publications

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“…This rate varies by up to 30% over portions of the temperature range from the Yu et al 27 value published in 1994. Recent transition state calculations 32 published in 1997 also agree more closely with the Yu et al value for k 1 . Simply changing k 1 in these mechanisms to the Yu et al value provides an improvement in terms of modeling our data.…”

Section: Resultssupporting

confidence: 78%

Shock tube measurements of branched alkane ignition times and OH concentration time histories

Oehlschlaeger

Davidson

Herbon

et al. 2003

Int J of Chemical Kinetics

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Ignition times and hydroxyl (OH) radical concentration time histories were measured behind reflected shock waves during the oxidation of three branched alkanes: iso-butane (2-methylpropane), iso-pentane (2-methylbutane), and iso-octane (2,2,4-trimethylpentane). Initial reflected shock conditions ranged from 1177 to 2009 K and 1.10 to 12.58 atm with dilute fuel/O 2 /Ar mixtures varying in fuel concentration from 100 ppm to 1.25% and in equivalence ratio from 0.25 to 2. Ignition times were measured using endwall CH emission and OH concentrations were measured using narrow-linewidth ring-dye laser absorption of the R 1 (5) line of the OH A-X (0,0) band at 306.7 nm. The ignition times and OH concentration time histories were compared to modeled predictions of seven branched alkane oxidation mechanisms currently available in the literature and the implications of these comparisons are discussed. These data provide a unique database for the validation of detailed hydrocarbon oxidation mechanisms of propulsion related fuels.

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Section: Resultssupporting

confidence: 78%

Shock tube measurements of branched alkane ignition times and OH concentration time histories

Oehlschlaeger

Davidson

Herbon

et al. 2003

Int J of Chemical Kinetics

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“…However, on the basis of CT calculations on the DMBE IV potential, about 50% backdissociation in Ref. 27 was postulated to be present between 200 and 5000 K. We, therefore, had to come back to the question of nonstatistical backdissociations. Doing complete CT calculations on our new ab initio surface, we come to the conclusion that our earlier assumption may have been premature.…”

Section: ͑13͒mentioning

confidence: 99%

Theoretical studies of the HO+O⇔HO2⇔H+O2 reaction. II. Classical trajectory calculations on an ab initio potential for temperatures between 300 and 5000 K

Troe

Ushakov

2001

The Journal of Chemical Physics

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A comparably simple new analytical expression of the potential energy surface for the HO+O⇔HO2⇔H+O2 reaction system is designed on the basis of previous high precision ab initio calculations along the minimum energy path of the HO2→H+O2 and HO2→HO+O dissociations. Thermal rate constants for the reaction HO+O→H+O2 are determined by extensive classical trajectory calculations. The results depend on the policy to solve the zeropoint energy problem. We show that, with the chosen policy, there are nearly equal amounts of statistical and nonstatistical backdissociations HO+O←HO2 following HO+O→HO2; however, backdissociations become important only at temperatures above about 500 K. Below 500 K, the reaction is completely capture-controlled. Below 300 K, classical trajectory treatments become inadequate, because quantum effects then are so important that only the quantum statistical adiabatic channel model gives reliable results. For the reaction HO+O→H+O2 and the range 300–5000 K, a rate constant of k/10−11 cm3 molecule−1 s−1=0.026(T/1000 K)1.47+1.92(1000 K/T)0.46 is obtained from the trajectory calculations. Converting experimental results for the reaction H+O2→HO+O to the reverse reaction on the basis of the revised enthalpy of formation of OH, agreement between experiment and theory within better than 20% is obtained between 300 and 5000 K.

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“…48 At first, only quasiclassical calculations were possible. [17][18][19][20][21][22][23][24][25][26][27] Only in the last five years have full quantum mechanical calculations become possible with most calculations performed for total angular momentum Jϭ0. [28][29][30][31][32][33][34][35][36][37][38] Whenever JϾ0 was studied, it was done using an approximate method.…”

Section: Introductionmentioning

confidence: 99%

Time-dependent quantum mechanical calculations on H+O2 for total angular momentum J>0 II: On the importance of Coriolis coupling

Meijer

Goldfield

1999

The Journal of Chemical Physics

112

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Articles you may be interested inTime-dependent quantum wave packet study of the Ar+H2 +→ArH++H reaction on a new ab initio potential energy surface for the ground electronic state (12 A′) Time-dependent quantum mechanical calculations on H+O 2 for total angular momentum J>0. III. Total cross sectionsThe HϩO 2 →OHϩO reaction has been studied for total angular momentum JϾ0 with a time-dependent wave packet method using the Coriolis coupled method of Goldfield and Gray ͓E. M. Goldfield and S. K. Gray, Comp. Phys. Commun. 98, 1 ͑1996͔͒ on parallel computers. Helicity conserving ͑HC͒ and coupled channel ͑CC͒ calculations were performed for Jϭ1, Jϭ2, Jϭ5, and Jϭ10 using two different embeddings for the body fixed coordinate system to investigate the importance of Coriolis coupling for this reactive system. If the H-O 2 distance is taken to be the z axis of the coordinate system, we find poor agreement between the HC and the CC calculations for JϾ2. When the O 2 bond is taken to be the z axis, we find good agreement between the CC and HC calculations at low J. For higher J the agreement gets progressively worse, especially at higher energies. We can explain these results using a classical model from a previous paper on HϩO 2 ͓A. J. H. M. Meijer and E. M. Goldfield, J. Chem. Phys. 108, 5404 ͑1998͔͒.

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Quantifying the non-RRKM effect in the H + O2 ? OH + O reaction

Cited by 64 publications

References 59 publications

Shock tube measurements of branched alkane ignition times and OH concentration time histories

Shock tube measurements of branched alkane ignition times and OH concentration time histories

Theoretical studies of the HO+O⇔HO2⇔H+O2 reaction. II. Classical trajectory calculations on an ab initio potential for temperatures between 300 and 5000 K

Time-dependent quantum mechanical calculations on H+O2 for total angular momentum J>0 II: On the importance of Coriolis coupling

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Quantifying the non-RRKM effect in the H + O2 ? OH + O reaction

Cited by 64 publications

References 59 publications

Shock tube measurements of branched alkane ignition times and OH concentration time histories

Shock tube measurements of branched alkane ignition times and OH concentration time histories

Theoretical studies of the HO+O⇔HO2⇔H+O2 reaction. II. Classical trajectory calculations on an ab initio potential for temperatures between 300 and 5000 K

Time-dependent quantum mechanical calculations on H+O2 for total angular momentum J&gt;0 II: On the importance of Coriolis coupling

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Time-dependent quantum mechanical calculations on H+O2 for total angular momentum J>0 II: On the importance of Coriolis coupling