Reaction of HO with CO: Tunneling Is Indeed Important

Nguyễn, Thanh Lâm; Xue, Bert C.; Weston, Ralph E.; Barker, John R.; Stanton, John F.

doi:10.1021/jz300443a

Cited by 97 publications

(157 citation statements)

References 30 publications

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“…The present data are consistent with the previous measurements from Frank and Just , Michael and Sutherland , Davidson et al , Oldenborg et al , and Krasnoperov and Michael . In addition, the present measurements are in excellent agreement with the non‐Arrhenius expression from GRI‐Mech 3.0 and the recent theoretical calculation using SCTST from Nguyen et al .…”

Section: Discussionsupporting

confidence: 92%

“…However, the values of k 1 from USC‐Mech v2.0 are ∼20% lower than the present measurements. Concurrently, Nguyen et al computed the rate constant for the title reaction with semiclassical transition state theory (SCTST), which implemented nonseparable coupling among all degrees of freedom (including the reaction coordinate) in the transition state region and multidimensional quantum mechanical tunneling along the curved reaction path. Their theoretical calculation (the black dashed line in Fig.…”

Section: Kinetic Measurementsmentioning

confidence: 99%

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A Shock Tube Study of H₂ + OH → H₂O + H Using OH Laser Absorption

Lam

Davidson

Hanson

2013

Int J of Chemical Kinetics

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The rate constant for the reaction of hydroxyl radicals (OH) with molecular hydrogen (H2) was measured behind reflected shock waves using UV laser absorption of OH radicals near 306.69 nm. Test gas mixtures of H2 and tert‐butyl hydroperoxide (TBHP) diluted in argon were shock‐heated to temperatures ranging from 902 to 1518 K at pressures of 1.15–1.52 atm. OH radicals were produced by rapid thermal decomposition of TBHP at high temperatures. The rate constant for the title reaction was inferred by best fitting the measured OH time histories with the simulated profiles from the comprehensive reaction mechanism of Wang et al. (USC‐Mech v2.0) (2007). The measured values can be expressed in the Arrhenius equation as k1(T) = 4.38 × 1013 exp(–3518/T) cm3 mol−1 s−1 over the temperature range studied. A detailed error analysis was performed to estimate the overall uncertainty of the title reaction, and the estimated (2 – σ) uncertainties were found to be ±17% at 972 and 1228 K. The present measurements are in excellent agreement with the previous experimental studies from Frank and Just (Ber Bunsen‐Ges Phys Chem 1985, 89, 181–187), Michael and Sutherland (J Phys Chem 1988, 92, 3853–3857), Davidson et al. (Symp (Int) Combust 1988, 22, 1877–1885), Oldenborg et al. (J Phys Chem 1992, 96, 8426–8430), and Krasnoperov and Michael (J Phys Chem A 2004, 108, 5643–5648).In addition, the measured rate constant is in close accord with the non‐Arrhenius expression from GRI‐Mech 3.0 (http://www.me.berkeley.edu/gri_mech/) and the theoretical calculation using semiclassical transition state theory from Nguyen et al. (Chem Phys Lett 2010, 499, 9–15).

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Section: Discussionsupporting

confidence: 92%

Section: Kinetic Measurementsmentioning

confidence: 99%

A Shock Tube Study of H₂ + OH → H₂O + H Using OH Laser Absorption

Lam

Davidson

Hanson

2013

Int J of Chemical Kinetics

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“…51 Rate constants obtained previously by our group for CH 4 + Cl using the CC-a//CC-a level of theory were in very good agreement with experimental data. 52 Previous theoretical studies of other reactions have also obtained accurate rate constants using CCSD(T) with Dunning basis sets, 52,53,54 The two levels of theory produced similar optimized geometries of reactants, complex and products, but the geometries and vibrational frequencies for the transition states differed significantly.…”

Section: Electronic Structurementioning

confidence: 99%

Comparison of Three Isoelectronic Multiple-Well Reaction Systems: OH + CH₂O, OH + CH₂CH₂, and OH + CH₂NH

Ali

Barker

2015

J. Phys. Chem. A

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Methylenimine (CH2NH) has been predicted to be a product of the atmospheric photo-oxidation of methylamine, but its atmospheric reactions have not been measured. In this paper, we report potential energy surfaces (PESs) and rate constants for OH + CH2NH and its isoelectronic analogues OH + CH2O and OH + CH2CH2, which are more fully understood. The PESs were computed using the BHandHLYP/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels of theory. Canonical variational transition state theory and Rice-Ramsperger-Kassel-Marcus and master equation modeling were used to calculate temperature- and pressure-dependent rate constants, with particular emphasis on the OH + reactant entrance channels and the effects of prereactive complexes. The computed results are in reasonable agreement with experimental data where they can be compared and also with the results of previous theoretical calculations. The results show that to some extent OH radicals both add to the carbon center double bond in CH2NH and abstract methylene hydrogen atoms, as in the OH + CH2O and OH + CH2CH2 reactions, respectively, but the dominant pathway is abstraction of the hydrogen from N-H. The computed rate constants are suitable for both atmospheric and combustion modeling.

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“…7 Because SCIs are readily consumed, they have very low steady-state concentrations, 8 and consequently their fate in the atmosphere is not well established. 1 To provide a relatively clean source of SCIs for spectroscopic, 9-21 dynamics, [22][23][24][25][26] and kinetics studies, [27][28][29][30][31][32][33][34][35][36] SCIs are almost exclusively made from photo-oxidation reactions of (R 1 R 2 )CI 2 in the presence of O 2 (where R 1 /R 2 represent hydrogen atoms or alkyl radicals To provide accurate rate constants and to aid experimental measurements, unimolecular decomposition rate constants of syn-CH 3 CHOO under atmospheric conditions are computed here from first principles using Miller's semiclassical transition state theory (SCTST) [41][42][43][44][45] in combination with a two-dimensional master equation (2DME) approach. 7,46 This chemical kinetics analysis is performed using a high accuracy potential energy surface that is constructed with a modification of the HEAT protocol.…”

Section: Introductionmentioning

confidence: 99%

Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

Nguyen

McCaslin

McCarthy

et al. 2016

The Journal of Chemical Physics

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The thermal decomposition of syn-ethanal-oxide (syn-CH 3 CHOO) through vinyl hydrogen peroxide (VHP) leading to hydroxyl radical is characterized using a modification of the HEAT thermochemical protocol. The isomerization step of syn-CH 3 CHOO to VHP via a 1,4 H-shift, which involves a moderate barrier of 72 kJ/mol, is found to be rate determining. A two-dimensional master equation approach, in combination with semi-classical transition state theory, is employed to calculate the time evolution of various species as well as to obtain phenomenological rate coefficients. This work suggests that, under boundary layer conditions in the atmosphere, thermal unimolecular decomposition is the most important sink of syn-CH 3 CHOO. Thus, the title reaction should be included into atmospheric modeling. The fate of cold VHP, the intermediate stabilized by collisions with a third body, has also been investigated. Published by AIP Publishing. [http://dx

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Reaction of HO with CO: Tunneling Is Indeed Important

Cited by 97 publications

References 30 publications

A Shock Tube Study of H₂ + OH → H₂O + H Using OH Laser Absorption

A Shock Tube Study of H₂ + OH → H₂O + H Using OH Laser Absorption

Comparison of Three Isoelectronic Multiple-Well Reaction Systems: OH + CH₂O, OH + CH₂CH₂, and OH + CH₂NH

Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

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Reaction of HO with CO: Tunneling Is Indeed Important

Cited by 97 publications

References 30 publications

A Shock Tube Study of H2 + OH → H2O + H Using OH Laser Absorption

A Shock Tube Study of H2 + OH → H2O + H Using OH Laser Absorption

Comparison of Three Isoelectronic Multiple-Well Reaction Systems: OH + CH2O, OH + CH2CH2, and OH + CH2NH

Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

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A Shock Tube Study of H₂ + OH → H₂O + H Using OH Laser Absorption

A Shock Tube Study of H₂ + OH → H₂O + H Using OH Laser Absorption

Comparison of Three Isoelectronic Multiple-Well Reaction Systems: OH + CH₂O, OH + CH₂CH₂, and OH + CH₂NH