Re-analysis of the ultraviolet absorption spectrum of ozone

O’Keeffe, Patrick; Ridley, Trevor; Lawley, Kenneth P.; Donovan, Robert J.

doi:10.1063/1.1412254

Cited by 27 publications

(42 citation statements)

References 35 publications

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“…The observed bending progression, however, is rather short. 5 In the present study we perform dynamics calculations using a new PES for the B state and demonstrate that the resulting spectrum of vibrational energies in the two C s wells as well as the corresponding intensities are in good agreement with the experimental spectrum. Our vibrational assignment mostly agrees with that of O'Keeffe et al, 5 which is the latest and the most complete experimental assignment.…”

supporting

confidence: 61%

“…The cross section is exceedingly small but increases by about four orders of magnitude within the range of the Huggins band. It shows a long progression of diffuse vibrational structures, the assignment of which has been debated for a long time; the ''history'' of this assignment recently was reviewed by O'Keeffe et al 5 Several points make a clear-cut assignment of the Huggins band difficult: doubts about the upper electronic state and therefore the topography of the relevant potential energy surface ͑PES͒, the diffuseness of the absorption features, and congestion because of hot bands.…”

mentioning

confidence: 99%

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The Huggins band of ozone: Unambiguous electronic and vibrational assignment

Qu¹,

Zhu²,

Tashiro³

et al. 2004

The Journal of Chemical Physics

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The Huggins band of ozone is investigated by means of exact dynamics calculations using a new ͑diabatic͒ potential energy surface for the 1 B 2 state. The remarkable agreement with the measured spectrum strongly suggests that the Huggins band is due to the two C s potential wells of the 1 B 2 state. The vibrational assignment, based on the nodal structure of wave functions, supports the most recent experimental assignment.

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supporting

confidence: 61%

mentioning

confidence: 99%

The Huggins band of ozone: Unambiguous electronic and vibrational assignment

Qu¹,

Zhu²,

Tashiro³

et al. 2004

The Journal of Chemical Physics

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“…An assignment of the diffuse structures in the measured spectrum in terms of only two modes, symmetric stretch and bending, has been suggested by O'Keeffe et al 19 At the present time we cannot judge whether this assignment is correct. However, the possibility of an assignment with only two modes indicates that in reality the motion of the wave packet is considerably simpler than in the one-state calculations: In the one-state model significant parts of the wave packet are trapped for too long, giving rise to an involved threedimensional motion.…”

Section: A Absorption Spectrummentioning

confidence: 62%

“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] The electronic structure of ozone is known to be complicated. 1 It has been experimentally studied in great detail over several decades 2,3 and is still under intense investigation.…”

Section: Introductionmentioning

confidence: 99%

The photodissociation of ozone in the Hartley band: A theoretical analysis

Zhu

Grebenshchikov

et al. 2005

The Journal of Chemical Physics

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Three-dimensional diabatic potential energy surfaces for the lowest four electronic states of ozone with 1A' symmetry-termed X, A, B, and R-are constructed from electronic structure calculations. The diabatization is performed by reassigning corresponding energy points. Although approximate, these diabatic potential energy surfaces allow one to study the uv photodissociation of ozone on a level of theory not possible before. In the present work photoexcitation in the Hartley band and subsequent dissociation into the singlet channel, O3X+hnu-->O(1D)+O2(a 1Deltag), are investigated by means of quantum mechanical and classical trajectory calculations using the diabatic potential energy surface of the B state. The calculated low-resolution absorption spectrum as well as the vibrational and rotational state distributions of O2(a 1Deltag) are in good agreement with available experimental results.

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“…In Table 1, we summarize the calculations for the vertical transition energies of ozone in the gas phase obtained at the multireference configuration interaction (MRCI) level. In the UV excitation range, the Hartley band originates from photoexcitation to the 1 1 B 2 and 2 1 A 2 electronic states (18,19), and the Huggins band involves the 2 1 A 1 electronic state (20). These two absorption bands shield Earth's surface from the harmful UV solar emissions, protecting living organisms from harmful radiation.…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic signatures of ozone at the air–water interface and photochemistry implications

Anglada

Martins‐Costa

Ruiz‐López

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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First-principles simulations suggest that additional OH formation in the troposphere can result from ozone interactions with the surface of cloud droplets. Ozone exhibits an affinity for the airwater interface, which modifies its UV and visible light spectroscopic signatures and photolytic rate constant in the troposphere. Ozone cross sections on the red side of the Hartley band (290-to 350-nm region) and in the Chappuis band (450-700 nm) are increased due to electronic ozone-water interactions. This effect, combined with the potential contribution of the O 3 + hν → O() photolytic channel at the interface, leads to an enhancement of the OH radical formation rate by four orders of magnitude. This finding suggests that clouds can influence the overall oxidizing capacity of the troposphere on a global scale by stimulating the production of OH radicals through ozone photolysis by UV and visible light at the air-water interface.atmospheric chemistry | heterogeneous processes | reactive oxidant species | computer simulations O zone, which is generated in the stratosphere, is well known to strongly absorb solar radiation in the UV region and contribute to the radiative forcing of the atmosphere, thereby influencing climate (1, 2). Changes in ozone abundances can perturb UV radiation levels in the atmosphere and at Earth's surface, and thus the extensive quantification of ozone distributions is critical to understanding its impact on the global environment. Stratospheric ozone distribution changes can affect the temperature in the stratosphere as well as impact photochemical processes in the troposphere. Tropospheric ozone can be produced photochemically in situ or transported down from the stratosphere. Tropospheric ozone exhibits significant radiative forcing, because O 3 is a greenhouse gas, but it also acts as a pollutant; its concentration is one of the measures to indicate the air quality worldwide.The photochemistry of ozone in the troposphere is, on the other hand, an important source of hydroxyl radicals, which are key to the chemistry of the atmosphere and determine the fate of anthropogenically emitted organic compounds (3). Hydroxyl radicals are mainly produced through the reactions Field measurements over the equatorial Pacific found significant variability of tropospheric ozone and hydroxyl radical concentrations, which has been suggested to affect the oxidizing efficiency of the troposphere (4). On the other hand, different experiments have suggested that current atmospheric models are missing a source of OH radicals. Discrepancies between models and observations in forested and polluted environments, for instance, indicated that OH chemistry is not fully understood (5-8). Frost and Vaida (9) were the first to propose that ozone in the low atmosphere could form a weakly bound complex with water, whose photodissociation could account for up to 15% of the available OH in the troposphere. The implicit assumption is that the long-wavelength absorption of ozone may be enhanced as a result of complexation with...

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Re-analysis of the ultraviolet absorption spectrum of ozone

Cited by 27 publications

References 35 publications

The Huggins band of ozone: Unambiguous electronic and vibrational assignment

The Huggins band of ozone: Unambiguous electronic and vibrational assignment

The photodissociation of ozone in the Hartley band: A theoretical analysis

Spectroscopic signatures of ozone at the air–water interface and photochemistry implications

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