Vibrational relaxation of O2(X 3 Σ–g, v = 9–13) by collisions with O2

Watanabe, Shinji; Usuda, Shin-ya; Fujii, Hidekazu; Hatano, Hiroyuki; Tokue, Ikuo; Yamasaki, Katsuyoshi

doi:10.1039/b702840g

Cited by 13 publications

(34 citation statements)

References 30 publications

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“…It agrees with some of the room temperature measured rate coefficients ͑v = 3 and 5͒ and overpredicts the measured rate coefficients for v = 2 and underpredicts those for v = 4. For O 2 ͑v =8͒ it agrees with the measurement of Park and Slanger 3 and gives a value smaller than the measurement of Klatt et al 5 and the calculation of Hernández et al 13 For O 2 ͑v = 9 and 10͒ the results of Klatt et al 5 and Hernández et al 13 agree with the measurements of Watanabe et al 37 Since our calculation has the formalism of near-resonant vibration-to-vibration ET mechanism, we did not feel that it should give reliable results for v Ն 9. Our calculation can be extended to the transfer of vibrational energy from O 2 to CO 2 without further assumption or modifications.…”

Section: Discussionsupporting

confidence: 83%

Vibrational energy transfer in O2(v=2–8)–O2(v=) collisions

Sharma¹,

Welsh²

2009

The Journal of Chemical Physics

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Starting with multipolar-multipolar interaction for intermolecular potential we have carried out a calculation of rate coefficients for transfer of one quantum of vibrational energy upon impact of O(2)(2 < or = v < or = 8) with O(2)(v = 0) as a function of temperature (150 K < or = T < or = 450 K). The equations for energy transfer, in the second order of perturbation theory, mediated by isotropic and anisotropic dispersion interactions, are derived. None of the parameters appearing in the calculation were adjusted to obtain agreement with the experimentally measured rate coefficients. The results of the calculation are compared with experimentally measured room temperature rate coefficients of the disappearance of O(2)(v) upon collision with O(2)(v = 0). The agreement is found to be good for the disappearance of O(2)(v = 3) and O(2)(v = 5). For O(2)(v = 2) the calculation gives a larger rate coefficient than the measured value, while for O(2)(v = 4) it gives a smaller value than obtained by measurement. For O(2)(v = 8) it agrees with one measurement and gives a value smaller than another measurement and a calculation.

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Section: Discussionsupporting

confidence: 83%

Vibrational energy transfer in O2(v=2–8)–O2(v=) collisions

Sharma¹,

Welsh²

2009

The Journal of Chemical Physics

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“…[19][20][21] It is well known that there are two main channels in the UV photolysis of O 3 at λ ≈ 250 nm 1,13,22 …”

Section: Methodsmentioning

confidence: 99%

Nascent Vibrational Energy Distributions of O₂(X³Σ_g⁻, v = 6−13) Generated in the Photolysis of O₃ at 266 nm

et al. 2009

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The vibrational levels of O2(X3Sigma(g)-) generated in the ultraviolet photolysis of O3 at 266 nm were detected via laser-induced fluorescence (LIF) of the B3Sigma(u)- - X3Sigma(g)- system. The nascent vibrational energy distributions of O2(X3Sigma(g)-, nu = 6-13) have been measured by two different methods. One is a kinetic analysis based on the originally developed integrated profiles method (IPM). The time-resolved LIF of a single vibrational level has been recorded in the presence of CF4 or O2 as a relaxation partner. The IPM analysis of the profiles gave the relative detectabilities of adjacent vibrational levels, and the initial relative populations of the vibrational levels have been determined from the intensities of LIF subsequent to the photolysis. The other is the analysis of the area intensities of the LIF of the vibrational levels of interest. The rotational levels with the identical quantum numbers of different vibrational levels in the X3Sigma(g)- state were excited to a common vibrational level nu' = 0 in the B3Sigma(u)- state. Correction for the LIF intensities with the Franck-Condon factors was made, and the initial relative populations have been obtained. The two different methods have given similar nascent vibrational energy distributions, and comparison to the previous reports has been made.

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“…The fact is that for such v' values in reaction (6), the energy transfer from the oxygen molecule to the nitrogen molecule has an almost resonant character. In both (5) and 6cases, it is obvious that a change in the reaction rate coefficient with a change in v is associated with a defect of the reaction energy (see Figure 4 where both experimental data [29,48,[50][51][52][53][54] and theoretical estimates [55] are presented). The smaller defect of energy, the greater the reaction rate coefficient.…”

Section: Energy Transfer In Collisional Reactionsmentioning

confidence: 99%

“…Rate coefficients of O2(X 3 Σg, v) + O2 → products[29,32,48,[50][51][52][53][54][55] and O2(X 3 Σg, v) + N2 → products[29] depending on module of energy mismatch. The numbers indicate values of the vibrational quantum.…”

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confidence: 99%

Model of Daytime Oxygen Emissions in the Mesopause Region and Above: A Review and New Results

Yankovsky

Vorobeva

2020

Atmosphere

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Atmospheric emissions of atomic and molecular oxygen have been observed since the middle of 19th century. In the last decades, it has been shown that emissions of excited oxygen atom O(1D) and molecular oxygen in electronically–vibrationally excited states O2(b1Σ+g, v) and O2(a1Δg, v) are related by a unified photochemical mechanism in the mesosphere and lower thermosphere (MLT). The current paper consists of two parts: a review of studies related to the development of the model of ozone and molecular oxygen photodissociation in the daytime MLT and new results. In particular, the paper includes a detailed description of formation mechanism for excited oxygen components in the daytime MLT and presents comparison of widely used photochemical models. The paper also demonstrates new results such as new suggestions about possible products for collisional reactions of electronically–vibrationally excited oxygen molecules with atomic oxygen and new estimations of O2(b1Σ+g, v = 0–10) radiative lifetimes which are necessary for solving inverse problems in the lower thermosphere. Moreover, special attention is given to the “Barth’s mechanism” in order to demonstrate that for different sets of fitting coefficients its contribution to O2(b1Σ+g, v) and O2(a1Δg, v) population is neglectable in daytime conditions. In addition to the review and new results, possible applications of the daytime oxygen emissions are presented, e.g., the altitude profiles O(3P), O3 and CO2 can be retrieved by solving inverse photochemical problems when emissions from electronically vibrationally excited states of O2 molecule are used as proxies.

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Vibrational relaxation of O2(X 3 Σ–g, v = 9–13) by collisions with O2

Cited by 13 publications

References 30 publications

Vibrational energy transfer in O2(v=2–8)–O2(v=) collisions

Vibrational energy transfer in O2(v=2–8)–O2(v=) collisions

Nascent Vibrational Energy Distributions of O₂(X³Σ_g⁻, v = 6−13) Generated in the Photolysis of O₃ at 266 nm

Model of Daytime Oxygen Emissions in the Mesopause Region and Above: A Review and New Results

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Vibrational relaxation of O2(X 3 Σ–g, v = 9–13) by collisions with O2

Cited by 13 publications

References 30 publications

Vibrational energy transfer in O2(v=2–8)–O2(v=) collisions

Vibrational energy transfer in O2(v=2–8)–O2(v=) collisions

Nascent Vibrational Energy Distributions of O2(X3Σg−, v = 6−13) Generated in the Photolysis of O3 at 266 nm

Model of Daytime Oxygen Emissions in the Mesopause Region and Above: A Review and New Results

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Nascent Vibrational Energy Distributions of O₂(X³Σ_g⁻, v = 6−13) Generated in the Photolysis of O₃ at 266 nm