Atmospheric quenching of vibrationally excited O2(1Δ)

Klais, Odo; Laufer, Allan H.; Kurylo, Michael J.

doi:10.1063/1.440483

Cited by 16 publications

(7 citation statements)

References 18 publications

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“…Collins and Husain 14 found the v = 1 levels of a 1 Δ g and of the ground-state X 3 Σ g − are strongly coupled, such that the reaction to produce O 2 (X 3 Σ g − , v = 1) and O 2 (a 1 Δ g , v = 0) and its reverse are very fast. Klais et al 15 concluded from their experiments that O 2 (a 1 Δ g , v = 1) removal in O 2 did not lead to enhanced production of O 2 (a 1 Δ g , v = 0), a significantly different conclusion than that of the earlier study. We will show the results of Collins and Husain are consistent with the more direct experimental data presented here.…”

Section: ■ Introductionmentioning

confidence: 65%

“…In earlier work, Klais et al detected the a 1 Δ g ( v = 2,3) levels in a flash photolysis experiment and found them to disappear very quickly, although ozone interference prevented the detection of v = 1, which we know disappears even faster. They monitored the buildup of a 1 Δ g ( v = 0) and found it to be relatively slow after its initial appearance and unaffected by the addition of O 2 .…”

Section: Discussionmentioning

confidence: 87%

“…The v = 1 level of the a 1 Δ g state has been previously studied , using vacuum ultraviolet absorption techniques to monitor the excited O 2 molecule. The investigators reached diametrically opposite conclusions as to the mechanism of relaxation of O 2 molecules in this level by collisions with ground-state O 2 .…”

Section: Introductionmentioning

confidence: 99%

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Laboratory Studies of Vibrational Excitation in O₂(a¹Δ_g, v) Involving O₂, N₂, and CO₂

et al. 2018

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Collisional removal of electronic energy from O 2 in the low-lying a 1 Δ g state is typically an extremely slow process for the v = 0 level. In this study, we report results on the deactivation of O 2 (a 1 Δ g , v = 1−3) in collisions with O 2 and CO 2 . Ozone photodissociation in the 200−310 nm Hartley band is the source of O 2 (a, v), and resonance-enhanced multiphoton ionization is used to probe the vibrational-level populations. Deactivation of the a(v = 1−3) levels in collisions with O 2 at 300 K is fast, with rate coefficients of (5.6 ± 1.1) × 10 −11 , (3.6 ± 0.4) × 10 −11 , and (1.9 ± 0.4) × 10 −11 cm 3 s −1 (2σ) for v = 1, 2, and 3, respectively. The relaxation process appears to involve a near-resonant electronic energy transfer pathway analogous to that observed in vibrationally excited O 2 (b 1 Σ g + ). With CO 2 collider gas, the removal rate coefficient at 300 K is (1.8 ± 0.4) × 10 −14 and (4.4 ± 0.6) × 10 −14 cm 3 s −1 (2σ) for v = 1 and 2, respectively. Despite the small mole fraction of O 2 in the atmospheres of Mars and Venus, O 2 is at least as important as CO 2 in the final stages of collisional relaxation within the O 2 vibrational-level manifold.

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Section: ■ Introductionmentioning

confidence: 65%

Section: Discussionmentioning

confidence: 87%

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Laboratory Studies of Vibrational Excitation in O₂(a¹Δ_g, v) Involving O₂, N₂, and CO₂

et al. 2018

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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%

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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“…The values of the rate constants of the reactions of deexcitation of electronically-vibrationally excited O 2 molecules O 2 (a 1 g , v≥1) at collisions with N 2 are so small that such processes do not affect the populations of electronicvibrational levels under consideration in comparison with the processes of deexcitation at collisions with molecular oxygen. For estimations we used the maximum value for these rate constants 8.4×10 −14 cm 3 s −1 from Klais et al (1980), which is two orders of magnitude smaller than the rate constants of the processes of deexcitation at collisions with molecular oxygen.…”

Section: Introductionmentioning

confidence: 99%

Model of daytime emissions of electronically-vibrationally excited products of O<sub>3</sub> and O<sub>2</sub> photolysis: application to ozone retrieval

Yankovsky

Manuilova

2006

Ann. Geophys.

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(X 3 − g , v). In contrast to the previous models of kinetics of O 2 (a 1 g ) and O 2 (b 1 + g ), our model takes into consideration the following basic facts: first, photolysis of O 3 and O 2 and the processes of energy exchange between the metastable products of photolysis involve generation of oxygen molecules on highly excited vibrational levels in all considered electronic states -b 1 + g , a 1 g and X 3 − g ; second, the absorption of solar radiation not only leads to populating the electronic states on vibrational levels with vibrational quantum number v equal to 0 -O 2 (b 1 + g , v=0) (at 762 nm) and O 2 (a 1 g , v=0) (at 1.27 µm), but also leads to populating the excited electronicvibrational states O 2 (b 1 + g , v=1) and O 2 (b 1 + g , v=2) (at 689 nm and 629 nm). The proposed model allows one to calculate not only the vertical profiles of the O 2 (a 1 g , v=0) and O 2 (b 1 + g , v=0) concentrations, but also the profiles of2)] and O 2 (X 3 − g , v=1-35). In the altitude range 60-125 km, consideration of the electronic-vibrational kinetics significantly changes the calculated concentrations of the metastable oxygen molecules and reduces the discrepancy between the altitude profiles of ozone concentrations retrieved from the 762-nm and 1.27-µm emissions measured simultaneously.

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Atmospheric quenching of vibrationally excited O2(1Δ)

Cited by 16 publications

References 18 publications

Laboratory Studies of Vibrational Excitation in O₂(a¹Δ_g, v) Involving O₂, N₂, and CO₂

Laboratory Studies of Vibrational Excitation in O₂(a¹Δ_g, v) Involving O₂, N₂, and CO₂

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

Model of daytime emissions of electronically-vibrationally excited products of O<sub>3</sub> and O<sub>2</sub> photolysis: application to ozone retrieval

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Atmospheric quenching of vibrationally excited O2(1Δ)

Cited by 16 publications

References 18 publications

Laboratory Studies of Vibrational Excitation in O2(a1Δg, v) Involving O2, N2, and CO2

Laboratory Studies of Vibrational Excitation in O2(a1Δg, v) Involving O2, N2, and CO2

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

Model of daytime emissions of electronically-vibrationally excited products of O&lt;sub&gt;3&lt;/sub&gt; and O&lt;sub&gt;2&lt;/sub&gt; photolysis: application to ozone retrieval

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Laboratory Studies of Vibrational Excitation in O₂(a¹Δ_g, v) Involving O₂, N₂, and CO₂

Laboratory Studies of Vibrational Excitation in O₂(a¹Δ_g, v) Involving O₂, N₂, and CO₂

Model of daytime emissions of electronically-vibrationally excited products of O<sub>3</sub> and O<sub>2</sub> photolysis: application to ozone retrieval