UV Photolysis of ClOOCl

Moore, Teresa A.; Okumura, Mitchio; Seale, James W.; Minton, Timothy K.

doi:10.1021/jp984410+

Cited by 42 publications

(74 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These scenarios are motivated by the error limit given in previous work (cf. ref 13) and the regime of error limits obtained from this work at 308 nm.…”

Section: Resultsmentioning

confidence: 76%

“…12,13 This is accomplished by considering the detection limits of both cations. The estimate of the detection limits is based on the cation signals strengths that are measured as voltage pulses by a digital oscilloscope, where the signals are loaded into 50 Ω.…”

Section: Resultsmentioning

confidence: 99%

“…12 More recently, Moore et al found experimental evidence for the photolysis channel according to eq 6. 13 They deduced from molecular beam experiments a 9:1 preference for the formation of 2Cl + O 2 (cf. channel (2)), where photolysis experiments were carried out at 248 and 308 nm, respectively.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ultraviolet Photolysis of the ClO Dimer

Plenge¹,

Flesch²,

Kühl³

et al. 2004

J. Phys. Chem. A

View full text Add to dashboard Cite

Photodissociation of the ClO dimer (ClOOCl) is studied in the ultraviolet regime (250 and 308 nm) under collision-free conditions. The primary photolysis products are probed by photoionization mass spectrometry. At both photolysis wavelengths, exclusively the formation of 2Cl + O 2 is observed, corresponding to a primary quantum yield γ Cl near unity. Considering the error limit of the experimental results one obtains γ Cl g 0.98 at 250 nm and γ Cl g 0.90 at 308 nm, respectively. At both photolysis wavelengths the pathway yielding ClO is not observed, corresponding to γ ClO e 0.02 at 250 nm and γ ClO e 0.10 at 308 nm. Sensitivity studies of these results with respect to ozone depletion in the stratosphere regarding photochemically induced ozone loss are discussed using model simulations. These simulations suggest that a change of γ Cl from 1.0 to 0.9 leads to a reduction of polar ozone loss of ∼5%.

show abstract

“…These scenarios are motivated by the error limit given in previous work (cf. ref 13) and the regime of error limits obtained from this work at 308 nm.…”

Section: Resultsmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Ultraviolet Photolysis of the ClO Dimer

Plenge¹,

Flesch²,

Kühl³

et al. 2004

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Laboratory and theoretical studies show, that excited states of ClOOCl are rapidly dissociative (Birk et al, 1989;Moore et al, 1999;Kaledin and Morokuma, 2000;Toniolo et al, 2001; Peterson and Francisco, 2004;Huang et al, 2011) and assume φ(λ) between 0.9 and 1. In Fig.…”

Section: O Sumińska-ebersoldt Et Al: Cloocl Photolysis At High Solamentioning

confidence: 99%

ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight

Suminska-Ebersoldt¹,

Lehmann

Wegner³

et al. 2012

Atmos. Chem. Phys.

View full text Add to dashboard Cite

Abstract. The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) J ClOOCl is a critical parameter in catalytic cycles destroying ozone (O 3 ) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in J ClOOCl . Previous investigations of the consistency of published J ClOOCl with atmospheric observations of chlorine monoxide (ClO) and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of J ClOOCl over the ClOOCl formation rate constant k rec . Here, we constrain the atmospherically effective J ClOOCl independent of k rec , using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from J ClOOCl based on the absorption spectrum proposed by Pope et al. (2007), but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009). In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm is not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005).

show abstract

“…The recommendation is based on direct measurements made by Talukdar et al [1284] using pulsed photolysis-laser induced fluorescence over the temperature range 248-418 K. The recommendation is in excellent agreement with the ratio k(OH + H 2 )/k(OH + HD) = 1.65±0.05 at 298 K reported by Ehhalt et al [433] when combined with the recommended k(OH + H 2 ). (Table: 06-2, Note: 06-2) Back to [551] suggest that the reaction rate is substantially influenced by tunneling. In taking account of the tunneling contribution the rate constant is found to reach a minimum value near room temperature.…”

Section: -41mentioning

confidence: 99%