An evaluation of autocatalytic ozone production from vibrationally excited oxygen in the middle atmosphere

Toumi, Ralf

doi:10.1007/bf00053610

Cited by 20 publications

(11 citation statements)

References 10 publications

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“…This new experimental finding has kept the interest in highly vibrationally excited oxygen as a source of ozone. Recent observations of a substantial yield of O 2 ͑vу26͒ from O 3 photolysis 5 and modeling studies 5,11 further confirm the potential importance of this reactive channel for stratospheric O 3 .…”

Section: Introductionmentioning

confidence: 84%

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State-selected vibrational relaxation rates for highly vibrationally excited oxygen molecules

Hernández¹,

Toumi²,

Clary³

1995

The Journal of Chemical Physics

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The state-selected vibrational relaxation rates in O2+O2 collisions, with one O2 molecule in a highly vibrationally excited state, have been calculated from first principles. The vibrationally close-coupled, rotationally infinite order sudden approximation has been used to treat the collision dynamics and a potential energy surface based on high quality ab initio calculations, which include the variation of the O2 vibrational coordinates, has been developed. The calculated relaxation rates are in good agreement with those obtained from experiment for 8≤v<26 but fail to reproduce the sharp increase observed experimentally for v≥26 indicating the onset of a new vibrational relaxation mechanism.

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Section: Introductionmentioning

confidence: 84%

“…The present work was originally motivated by a recently proposed model [1][2][3][4][5] of autocatalytic production of ozone in the upper stratosphere and mesosphere. In this model molecular oxygen in a highly excited vibrational state, O 2 (X 3 ⌺ g Ϫ ,v), becomes a source of ozone via photodissociation followed by recombination:…”

Section: Introductionmentioning

confidence: 99%

State-selected vibrational relaxation rates for highly vibrationally excited oxygen molecules

Hernández¹,

Toumi²,

Clary³

1995

The Journal of Chemical Physics

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“…This reaction involves the triplet O 4 interaction, and the experimental activation energy of the reverse reaction R2. This PES does not take into account other short-range interactions for the four-body term or information on the transition state, frequencies, and geometry.…”

Section: Potential Energy Surfacementioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] A good example is an improved understanding of the ''ozone deficit'' problem, 2,[20][21][22][23] where there are significant discrepancies between observed and predicted ozone concentrations. In the course of experimental studies on the O 2 (X 3 ⌺ g Ϫ ,)ϩO 2 (X 3 ⌺ g Ϫ ,ϭ0) vibrational relaxation problem done by Wodtke's group, it has been found that vibrational quenching rate constants of O 2 rise to surprisingly high values above у25.…”

Section: Introductionmentioning

confidence: 99%

Reactive scattering of highly vibrationally excited oxygen molecules: Ozone formation?

Lauvergnat¹,

Clary²

1998

The Journal of Chemical Physics

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A new mechanism for the production of highly vibrationally excited OH in the mesosphere: An ab initio study of the reactions of O 2 ( A Σ u + 3 and A ′ Δ u 3 ) + H High level ab initio molecular orbital theory study of the structure, vibrational spectrum, stability, and low-lying excited states of HOONO A theoretical simulation of the 1s→2π excitation and deexcitation spectra of the NO molecule A new ab initio potential energy surface based on an internally contracted multireference configuration-interaction wave function is constructed for the O 2 (X 3 ⌺ g Ϫ ,)ϩO 2 (X 3 ⌺ g Ϫ ,ϭ0) →O 3 (X 1 A 1 )ϩO( 3 P) reaction with Ͼ20. The vibrational state-to-state reaction probabilities are calculated with a time independent reactive scattering method. The state selected reactive rate constants calculated with 2D reduced dimensionality theory are very small, suggesting that the reaction of ozone formation is not significant in the O 2 (X 3 ⌺ g Ϫ ,)ϩO 2 (X 3 ⌺ g Ϫ ,ϭ0) collision.

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“…The impact of vibrational excitation on atmospheric chemistry has been investigated extensively for vibrationally excited O 2 (e.g. Slanger et al, 1988;Toumi et al, 1991;Toumi, 2008;Shi and Barker, 1992;Mlynczak and Solomon, 1993;Slanger, 1994;Miller et al, 1994;Patten Jr. et al, 1994;Toumi et al, 1996;Zipf and Prasad, 1998) Hierl et al, 1997;Delmdahl et al, 1998;Varandas and Zhang, 2001;Varandas, 2002Varandas, , 2004aChen and Marcus, 2006;Vadas and Fritts, 2008;Prasad and Zipf, 2008), and results were in some cases under heavy dispute (Smith and Copeland, 2004;Varandas, 2005). Atmospheric chemistry models, particularly those developed for stratospheric ozone chemistry and later extended towards the upper atmosphere, usually neglect this effect (e.g., SLIMCAT, Chipperfield, 1999;MOZART, Horowitz et al, 2003;MESSy, Jöckel et al, 2005;REPROBUS, Lefèvre et al, 1994;CLAMS, McKenna et al, 2002).…”

Section: Introductionmentioning

confidence: 99%

Do vibrationally excited OH molecules affect middle and upper atmospheric chemistry?

et al. 2010

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Abstract. Except for a few reactions involving electronically excited molecular or atomic oxygen or nitrogen, atmospheric chemistry modelling usually assumes that the temperature dependence of reaction rates is characterized by Arrhenius' law involving kinetic temperatures. It is known, however, that in the upper atmosphere the vibrational temperatures may exceed the kinetic temperatures by several hundreds of Kelvins. This excess energy has an impact on the reaction rates. We have used upper atmospheric OH populations and reaction rate coefficients for OH(v = 0...9)+O 3 and OH(v = 0...9)+O to estimate the effective (i.e. population weighted) reaction rates for various atmospheric conditions. We have found that the effective rate coefficient for OH(v = 0...9)+O 3 can be larger by a factor of up to 1470 than that involving OH in its vibrational ground state only. At altitudes where vibrationally excited states of OH are highly populated, the OH reaction is a minor sink of O x and O 3 compared to other reactions involving, e.g., atomic oxygen. Thus the impact of vibrationally excited OH on the ozone or O x sink remains small. Among quiescent atmospheres under investigation, the largest while still small (less than 0.1%) effect was found for the polar winter upper stratosphere and mesosphere. The contribution of the reaction of vibrationally excited OH with ozone to the OH sink is largest in the upper polar winter stratosphere (up to 4%), while its effect on the HO 2 source is larger in the lower thermosphere (up to 1.5% for polar winter and 2.5% for midlatitude night conditions). For OH(v = 0...9)+O the effective rate coefficients are Correspondence to: T. von Clarmann (thomas.clarmann@kit.edu) lower by up to 11% than those involving OH in its vibrational ground state. The effects on the odd oxygen sink are negative and can reach −3% (midlatitudinal nighttime lowermost thermosphere), i.e. neglecting vibrational excitation overestimates the odd oxygen sink. The OH sink is overestimated by up to 10%. After a solar proton event, when upper atmospheric OH can be enhanced by an order of magnitude, the excess relative odd oxygen sink by consideration of vibrational excitation in the reaction of OH(v = 0...9)+O 3 is estimated at up to 0.2%, and the OH sink by OH(v = 0...9)+O can be reduced by 12% in the thermosphere by vibrational excitation.

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An evaluation of autocatalytic ozone production from vibrationally excited oxygen in the middle atmosphere

Cited by 20 publications

References 10 publications

State-selected vibrational relaxation rates for highly vibrationally excited oxygen molecules

State-selected vibrational relaxation rates for highly vibrationally excited oxygen molecules

Reactive scattering of highly vibrationally excited oxygen molecules: Ozone formation?

Do vibrationally excited OH molecules affect middle and upper atmospheric chemistry?

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