Vibrational rate enhancement in the reaction OH + H2(ν = 1) → H2O + H

Zellner, R.; Steinert, W

doi:10.1016/0009-2614(81)80465-4

Cited by 82 publications

(32 citation statements)

References 13 publications

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“…On the other hand vibrational excitation of H2 has a significant effect on the reaction rate. Zellner and Steinert [40] have used the DF-RF technique, with H2(v=l) formed by passing H2 over a heated tungsten filament and its concentration determined by vacuum U.V. absorption (Lymau transition), to determine k(29s) = (4.03=1.8) x 1011, for the reaction of OH(v=0) with H2(v=l).…”

Section: A Reactions With H2 and D2mentioning

confidence: 99%

Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos

Singleton

1988

Reviews of Chemical Intermediates

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Section: A Reactions With H2 and D2mentioning

confidence: 99%

Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos

Singleton

1988

Reviews of Chemical Intermediates

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“…7 along with experimental data 24,25 and results from previous theoretical studies. 9,11 In the present study, the OH vibration was treated thermally, though we also found that restricting the OH vibration in the ground state only yields negligible differences in the rate.…”

Section: Oh؉h 2 (Vј‫)1؍‬ Reactionmentioning

confidence: 83%

“…Our predicted enhancement factors ranging from 180 to 88.7 at various levels of theory, namely CVT, CVT/ZCT, and CVT/SCT, listed in Table II are within the experimental uncertainty that ranges from 80 to 193. 24,25 It has been known that the conventional transition state theory plus Wigner tunneling correction ͑TST/W͒ significantly overestimates the enhancement factor. This is due to the reason as pointed out in Truhlar and Isaacson's study 9 that the dynamical bottlenecks for the OHϩH 2 ͑vЈϭ1͒ are shifted significantly away from the saddle point toward the reactants.…”

Section: Oh؉h 2 (Vј‫)1؍‬ Reactionmentioning

confidence: 99%

“…1-15 This is because ͑i͒ the OHϩH 2 reaction is an important process in combustion chemistry, ͑ii͒ its small size permits accurate quantum scattering calculations to be carried out, 6,11,12 ͑iii͒ there exists a reasonably accurate ab initio potential energy function ͑PEF͒, denoted as Schatz-Elgersma ͑SE͒ PEF, 4 for this reaction, and ͑iv͒ experimental thermal rate constants, 16 -23 kinetic isotope effects, 18 and rate constants for vibrational excitations of either reactant are available. 24,25 In fact, it has been known experimentally that OH vibrational excitation has a negligible effect on the rate of reaction ͑R1͒ 26 whereas H 2 vibrational excitation was found to enhance the rate by a factor of 120Ϯ40 by Zellner and Steiner, 25 and a factor of 155Ϯ38 by Glass and Chaturvedi 24 at 298 K. Theoretical studies of the vibrational mode specific rate enhancements so far have some mixed success. All previous theoretical studies correctly predicted the small rate enhancement due to the excitation of the OH stretch.…”

Section: Introductionmentioning

confidence: 99%

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Direct ab initio dynamics studies of vibrational-state selected reaction rate of the OH+H2→H+H2O reaction

Truong

1995

The Journal of Chemical Physics

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Statisticaldiabatic model for stateselected reaction rates. Theory and application of vibrationalmode correlation analysis to OH(n OH)+H2(n HH)→H2O+HA comparative study of the reaction dynamics of the O(3 P)+H2→OH+H reaction on several potential energy surfaces. III. Collinear exact quantum transmission coefficient correction to transition state theory A comparative study of the reaction dynamics of several potential energy surfaces for O(3 P)+H2→OH+H. II. Collinear exact quantum and quasiclassical reaction probabilitiesWe present direct ab initio dynamics studies of vibrational-state selected reaction rates of the OHϩH 2 →HϩH 2 O reaction. Rate constants for both the OHϩH 2 ͑vϭ1͒ and OH͑vϭ1͒ϩH 2 reactions were calculated based on a full variational transition state theory plus multidimensional semiclassical tunneling approximations within a statistical diabatic model. The potential energy surface information was calculated at an accurate level of molecular orbital theory. In particular, geometries and frequencies along the minimum energy path were calculated at the quadratic configuration interaction level including all single and double excitations ͑QCISD͒ with the 6-311ϩG(d,p) basis set. Energies along the minimum energy path were further improved by a series of single point projected fourth-order Möller-Plesset perturbation theory ͑PMP4͒ calculations using the 6-311ϩϩG(2d f ,2pd) basis set. Our present results of vibrational excited state rate enhancements agree very well with previous experimental data. In view of these results, we also discuss the accuracy of the Schatz-Elgersma potential energy function in more detail.

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“…The inefficient removal of both OHt(1) and OHt(9) by H2 is reasonable since energy transfer is expected to be slow, and in the case of reaction, the vibrational energy resides in the bond which is not being broken. Recent studies [37,38] have shown that when H2 is vibrationally excited, the rate constant is in fact increased by over two orders of magnitude compared to the ground-state reaction.…”

Section: Comparison To Studies Of O H F ( 1 )mentioning

confidence: 99%

Relative rate constants for removal of vibrationally excited OH(X²π_i)_v=9 by some small molecules at room temperature

Finlayson-Pitts

Toohey

Ezell

1983

Int J of Chemical Kinetics

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Vibrationally excited OH in u = 9 [designated OHf(9)] was generated by the reaction of hydrogen atoms with ozone in a fast-flow discharge system at 300 f 3 K and a total pressure of 1.1 f 0.1 torr, with argon as the carrier gas. The addition of a species X, which can deactivate the OHt(9) or react with it, led to a decrease in the Meinel band chemiluminescent emission intensities at both 626 nm (9 -3 band) and 519 nm (9 -2 band), which were monitored as a function of the concentration of X. Application of the kinetic scheme developed previously for this chemical system gave the relative rate constant for the removal of OHt (9) fO.Ol;N203.5f0.4;N017.7f 1.5;H2074.3+2.9;DzO57.6f2.0;NH361.3f1.9;ND358.7 f 1.6; SO2 7.1 f 1.4; COS 8.4 f 1.7; H2S 33.7 f 8.4; CHa 1.56 f 0.03; CDI 1.06 f 0.06. Application of these relative rate constants to conditions in the upper atmosphere (60-100 km) suggests that OHt(9) is removed primarily by deactivation by 0 2 , and at altitudes 290 km, possibly by O(3P). However, since 0 2 is unusually efficient for a homonuclear diatomic in deactivating OH+(9), it may not be the primary deactivator for the lower ( u _< 8) vibrational levels. These results are compared to earlier studies of OHt (9), and possible mechanisms of interaction of OHt(9) with these molecules are discussed.

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Vibrational rate enhancement in the reaction OH + H2(ν = 1) → H2O + H

Cited by 82 publications

References 13 publications

Reactions of OH radicals with inorganic compounds in the gas phase

Reactions of OH radicals with inorganic compounds in the gas phase

Direct ab initio dynamics studies of vibrational-state selected reaction rate of the OH+H2→H+H2O reaction

Relative rate constants for removal of vibrationally excited OH(X²π_i)_v=9 by some small molecules at room temperature

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Vibrational rate enhancement in the reaction OH + H2(ν = 1) → H2O + H

Cited by 82 publications

References 13 publications

Reactions of OH radicals with inorganic compounds in the gas phase

Reactions of OH radicals with inorganic compounds in the gas phase

Direct ab initio dynamics studies of vibrational-state selected reaction rate of the OH+H2→H+H2O reaction

Relative rate constants for removal of vibrationally excited OH(X2πi)v=9 by some small molecules at room temperature

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Relative rate constants for removal of vibrationally excited OH(X²π_i)_v=9 by some small molecules at room temperature