The UV absorption of ClO Part 1. The A2Π–X2Π spectrum at wavelengths from 285–320 nm studied by cavity ring-down spectroscopy

Howie, Wendy H.; Lane, Ian C.; Newman, Stuart M.; Johnson, David A.; Orr-Ewing, Andrew J.

doi:10.1039/a903314i

Cited by 26 publications

(28 citation statements)

References 22 publications

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“…Our results are in reasonable agreement with the lifetimes reported in previous high-resolution spectroscopic studies, as indicated in Table II. [11][12][13] The differences between the lifetimes estimated using Eq. ͑14͒ and the lifetimes reported from line broadening measurements are not unexpected.…”

Section: Photodissociation Of Clo Below the O" 1 D 2 … Thresholdmentioning

confidence: 99%

“…Predissociation lifetimes for specific vibrational levels of the A 2 ⌸ ⍀ state predissociation based on spectral linewidths have been previously reported. [11][12][13] A theoretical treatment of the predissociation was first made by Bunker and Klein. 14 The authors neglected a rotational contribution to the predissociation lifetime and predicted predissociation rates using the spin-orbit interaction between A 2 ⌸ ⍀ state and a single repulsive state corre-lating to ground-state atoms.…”

Section: Introductionmentioning

confidence: 99%

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The UV photodissociation dynamics of ClO radical using velocity map ion imaging

Kim

Park

Niday

et al. 2005

The Journal of Chemical Physics

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We have studied the wavelength-dependent photodissociation dynamics of jet-cooled ClO radical from 235 to 291 nm using velocity map ion imaging. We find that Cl(2P(3/2))+O(1D(2)) is the dominant channel above the O(1D(2)) threshold with minor contributions from the Cl(2P(J))+O(3P(J)) and Cl(2P(1/2))+O(1D(2)) channels. We have measured the photofragment angular distributions for each dissociation channel and find that the A 2pi state reached via a parallel transition carries most of the oscillator strength above the O(1D(2)) threshold. The formation of O(3P(J)) fragments with positive anisotropy is evidence of curve crossing from the A 2pi state to one of several dissociative states. The curve crossing probability increases with wavelength in good agreement with previous theoretical calculations. We have directly determined the O(1D(2)) threshold to be 38,050+/-20 cm(-1) by measuring O(1D(2)) quantum yield in the wavelength range of 260-270 nm. We also report on the predissociation dynamics of ClO below the O(1D(2)) threshold. We find that the branching ratio of Cl(2P(3/2))/Cl(2P(1/2)) is 1.5+/-0.1 at both 266 and 291 nm. The rotational depolarization of the anisotropy parameters of the Cl(2P(3/2)) fragments provides predissociation lifetimes of 1.5+/-0.2 ps for the 9-0 band and 1.0+/-0.4 ps for the 8-0 band, in reasonable agreement with previous spectroscopic and theoretical studies.

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Section: Photodissociation Of Clo Below the O" 1 D 2 … Thresholdmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The UV photodissociation dynamics of ClO radical using velocity map ion imaging

Kim

Park

Niday

et al. 2005

The Journal of Chemical Physics

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“…êa;¸!.Ð5 ¦ §¥ìÉh;, ÿ.Ð5 ClO, OClO, BrO 7 OBrO ¥xëàÞ §Þ;. ;qf~à [25] ¢&bà [10,12] wè ]à [26,27] +Í{àw/ [28] ;ø ClO BrO à, Qø¯6øÁÒ ClO, BrO ú. Õ § E § Þ [33 35] . Peterson [36 38]…”

Section: Clo ¹ Bro üü;mentioning

confidence: 99%

平流层中臭氧耗减化学研究进展

李¹,

周²,

王³

2001

Chin. Sci. Bull.

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“…11 Ab initio calculations suggest that the principal candidates for states which predissociate the A 2 ⌸ i state are the 1 4 ⌺ ϩ , 2 4 ⌺ Ϫ , and 3 2 ⌸ states. [10][11][12] There have only been two direct experimental studies of the UV photodissociation of the ClO radical. Davis and Lee studied the photolysis at 248 nm using molecular beam neutral time-of-flight ͑TOF͒ and concluded that channel 2 was the dominant channel.…”

Section: Introductionmentioning

confidence: 98%

The ultraviolet photodissociation of jet-cooled ClO and BrO radicals

Zou

Kim

North

2002

The Journal of Chemical Physics

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Articles you may be interested inPhotodissociation of the BrO radical using velocity map ion imaging: Excited state dynamics and accurate D 0 0 ( Br O ) evaluation Resonance enhanced multiphoton ionization/time-of-flight measurements of the velocity and internal energy content of thermal and photochemical methyl radical sources Rev.The photodissociation dynamics of jet-cooled ClO and BrO radicals have been studied using resonance-enhanced multiphoton ionization with time-of-flight mass spectrometry. Four asymptotic electronic channels are energetically allowed for ClO photodissociation at 235 nm, although the dominant products observed at 235 nm are Cl( 2 P 3/2 ) and O( 1 D 2 ). Polarization-dependent time-of-flight profiles indicate that this channel has an anisotropy parameter of ␤ϭ1.2Ϯ0.2. Evidence for O( 3 P J ) products was detected in coincidence with Cl( 2 P 1/2 ) fragments, and we estimate that this channel constitutes Ͻ3% at this wavelength. In the photodissociation of BrO at 355 nm we observe two asymptotic electronic state channels, Br( 2 P 3/2 )ϩO( 3 P 2 ) and Br( 2 P 1/2 ) ϩO( 3 P 2 ) in a 0.75:0.25 ratio. Both channels have an anisotropy parameter of ␤ϭ1.5Ϯ0.1. Based on the measured asymptotic velocities of both channels, we have directly determined the Br-O bond dissociation energy to be 55.8Ϯ1.0 kcal/mol, providing a heat of formation for the BrO radical at 298 K of 29.7Ϯ1.0 kcal/mol in good agreement with previous spectroscopic determinations.

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The UV absorption of ClO Part 1. The A2Π–X2Π spectrum at wavelengths from 285–320 nm studied by cavity ring-down spectroscopy

Cited by 26 publications

References 22 publications

The UV photodissociation dynamics of ClO radical using velocity map ion imaging

The UV photodissociation dynamics of ClO radical using velocity map ion imaging

平流层中臭氧耗减化学研究进展

The ultraviolet photodissociation of jet-cooled ClO and BrO radicals

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