The formation of ClOO following the photoexcitation of aqueous OClO studied by two-color, time-resolved resonance Raman spectroscopy

Thomsen, Carsten; Philpott, Matthew P.; Hayes, Sophia C.; Reid, Philip J.

doi:10.1063/1.480540

Cited by 36 publications

(24 citation statements)

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“…TRRR studies of aqueous OClO using pump and probe wavelengths of 390 and 260 nm, respectively, were performed to determine whether ClOO is formed in solution consistent with the solid‐phase studies. ( 45,46,82 ) This probe wavelength falls within the absorption band of ClOO providing for resonant enhancement of the Raman scattering from this species. Figure 5A shows TRRR Stokes difference spectra of aqueous OClO ( 46 ).…”

Section: Chlorine Dioxidementioning

confidence: 96%

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The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

Cooksey

Reid

2004

Photochem & Photobiology

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Recent progress in understanding the phasedependent reactivity of halooxides and nitrosyl halides is outlined. Halooxide reactivity is represented by the photochemistry of chlorine dioxide (OCIO) and dichlorine monoxide (ClOCl). The gas phase photochemical dynamics of OClO are contrasted with the dynamics in condensed environments. The role of excited-state symmetry in defining the reaction dynamics and the observation of photoisomerization resulting in the production of ClOO are discussed. The current understanding of the excited-state reaction dynamics of ClOCl and evidence for photoisomerization of this species resulting in the production of ClClO are outlined. Finally, the photochemical reaction dynamics of the nitrosyl halide ClNO are presented. The main difference between the gas and condensed phase reaction dynamics of this species is that whereas photodissociation to form Cl and NO dominates the gas phase reaction dynamics, photoisomerization resulting in ClON production occurs to an appreciable extent in condensed environments. The observation of photoisomerization for OClO, ClOCl and ClNO suggests that this process is a general feature of the condensed phase reaction dynamics for smaller halooxides and nitrosyl halides. Finally, future areas for study in both halooxide and nitrosyl halide photoreactivity are outlined.

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Section: Chlorine Dioxidementioning

confidence: 96%

“…Time‐resolved resonance Raman (TRRR) studies have been performed to further probe the details of geminate recombination and photoproduct formation in OClO photochemistry ( 46,81–83 ). The first TRRR studies performed on aqueous OClO used excitation at 390 nm and a probe field at this same wavelength ( 83 ).…”

Section: Chlorine Dioxidementioning

confidence: 99%

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

Cooksey

Reid

2004

Photochem & Photobiology

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“…The kinetics for the formation of ClOO from Cl + O 2 reaction and decomposition of ClOO radicals have been investigated extensively both experimentally and theoretically. [5][6][7][8][9][10][11][12][13][14] Along with ClO x radicals, NO x (x = 1,2) are also very important in ozone destruction processes; 15 their interaction is of great relevance to the stratospheric chemistry.…”

Section: Introductionmentioning

confidence: 99%

Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

Raghunath

Lin

2012

The Journal of Chemical Physics

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The kinetics and mechanism for the reaction of ClOO with NO have been investigated by ab initio molecular orbital theory calculations based on the CCSD(T)/6-311+G(3df)//PW91PW91∕6-311+G(3df) method, employed to evaluate the energetics for the construction of potential energy surfaces and prediction of reaction rate constants. The results show that the reaction can produce two key low energy products ClNO + (3)O(2) via the direct triplet abstraction path and ClO + NO(2) via the association and decomposition mechanism through long-lived singlet pc-ClOONO and ClONO(2) intermediates. The yield of ClNO + O(2) ((1)△) from any of the singlet intermediates was found to be negligible because of their high barriers and tight transition states. As both key reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our transition state theory and Rice-Ramspergen-Kassel-Marcus/master equation calculations. The rate constants for ClNO + (3)O(2) and ClO + NO(2) production from ClOO + NO can be given by 2.66 × 10(-16) T(1.91) exp(341/T) (200-700 K) and 1.48 × 10(-24) T(3.99) exp(1711/T) (200-600 K), respectively, independent of pressure below atmospheric pressure. The predicted total rate constant and the yields of ClNO and NO(2) in the temperature range of 200-700 K at 10-760 Torr pressure are in close agreement with available experimental results.

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“…[5][6][7] However, the photochemical production of the ClOO isomer is observed in low-temperature matrixes, [8][9][10] and photolysis of solution-phase OClO results in both ClO/O and ClOO production. [11][12][13][14][15][16][17][18][19][20][21] Another halooxide, dichlorine monoxide (ClOCl), demonstrates phase-dependent photochemical reactivity similar to OClO. In the gas phase, direct dissociation to form Cl and ClO is the dominant photochemical pathway, [22][23][24][25][26][27][28][29][30] whereas, photoexcitation in low-temperature matrixes and in solution results in the formation of the isomer, ClClO.…”

Section: Introductionmentioning

confidence: 99%

Femtosecond Pump−Probe Studies of Nitrosyl Chloride Photochemistry in Solution

2006

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We present a femtosecond pump-probe study of the primary events of nitrosyl chloride (ClNO) photochemistry in solution. Following 266 nm photolysis, the resulting evolution in optical density is measured for ClNO dissolved in acetonitrile, chloroform, and dichloromethane. The results demonstrate that photolysis results in the production of a photoproduct that has an absorption band maximum at 295 nm in acetonitrile and 330 nm in chloroform and dichloromethane. To determine the extent of Cl production, comparative photochemical studies of methyl hypochlorite (MeOCl) and ClNO are performed. Photolysis of MeOCl in solution results in the production of the Cl:solvent charge-transfer complex; therefore, a comparison of the spectral evolution observed following MeOCl and ClNO photolysis under identical photolysis conditions is performed to determine the extent of Cl production following ClNO photolysis. We find that similar to the gas-phase photochemistry, Cl and NO formation is the dominant photochemical channel in acetonitrile. However, the photochemistry in chloroform and dichloromethane is more complex, with a second product formed in addition to Cl and NO. It is proposed that in these solvents photoisomerization also occurs, resulting in the production of ClON. The results presented here represent the first detailed examination of the solution phase photochemistry of ClNO.

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The formation of ClOO following the photoexcitation of aqueous OClO studied by two-color, time-resolved resonance Raman spectroscopy

Cited by 36 publications

References 32 publications

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

Femtosecond Pump−Probe Studies of Nitrosyl Chloride Photochemistry in Solution

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The formation of ClOO following the photoexcitation of aqueous OClO studied by two-color, time-resolved resonance Raman spectroscopy

Cited by 36 publications

References 32 publications

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides¶

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides¶

Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

Femtosecond Pump−Probe Studies of Nitrosyl Chloride Photochemistry in Solution

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The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶

The Phase‐dependent Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides^¶