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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5670-5679 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A pulsed laser photolysis technique has been employed to study the kinetics of the important stratospheric reaction O+ClO→k1Cl+O2 in N2 buffer gas over the temperature and pressure ranges 231–367 K and 25–500 Torr. 351 nm pulsed laser photolysis of Cl2/O3/N2 mixtures produced Cl atoms in excess over O3. After a delay sufficient for the reaction Cl+O3→ClO+O2 to go to completion, a small fraction of the ClO was photolyzed at 266 nm to produce O(3P). The decay of O(3P) in the presence of an excess, known concentration of ClO was then followed by time-resolved resonance fluorescence spectroscopy. We find that k1 is independent of pressure, but that k1(T) increases with decreasing temperature. Our results suggest that the Arrhenius expression k1(T)=(1.55±0.33)×10−11 exp{(263±60)/T} cm3 molecule−1 s−1 is appropriate for modeling stratospheric chemistry. Errors in the Arrhenius expression are 2σ and represent precison only. The absolute accuracy of k1 at any temperature within the range studied is estimated to be ±20%. Our results agree with other recent measurements of k1 at 298 K but give significantly faster rate coefficients at stratospheric temperatures. A few measurements of the rate coefficient for the reaction ClO+ClO→k7products were also carried out. These measurements were necessary to assess the time dependence of [ClO].
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 7050-7058 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A tunable pulsed dye laser was used to pump OD to the (A 2∑+,v′=1) level. The fluorescence excitation spectrum of OD in the wavelength region 287.26–290.03 nm in the A→X system was recorded. The rate coefficients for quenching of OD (A 2∑+) from v′=0 and v′=1 levels by O2, N2, air, and SF6 were measured. The rate coefficient for vibrational relaxation of OD (A 2∑+) from v′=1 to v′=0 level was separated from the overall rate coefficient for quenching of OD (A 2∑+) from v′=1 level to the ground (X 2Π) state for the above four gases. The rate coefficients for quenching of OD (A 2∑+) from v′=0 level to the ground (X 2Π) state by 15 common gases were measured by using excess SF6 to rapidly quench the OD (A 2∑+) from v′=1 to v′=0 level. All measurements were carried out in excess helium and are for rotationally thermalized OD (A 2∑+) radicals.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 3244-3251 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The quantum yields for the formation of O(1D) and O(3P) from the photolysis of ozone have been measured at 222 and 193 nm. The quantum yield for O(3P) was observed to be Φ(3P)=0.13±0.02 at 222 nm, and the primary quantum yield for O(1D) was found to be Φ(1D)=0.87±0.04. This measurement is consistent with other studies of O3 photolysis within the Hartley band which indicate that a significant portion (5–15%) of the products are formed in the ground state. At 193 nm the quantum yield for the production of excited state O(1D) atoms is Φ(1D)=0.46±0.29, which is significantly less than what is observed during photolysis within the lower energy Hartley band. The quantum yield for O(3P) atoms at 193 nm was found to be 0.57±0.14. We have also observed that the quantum yield for O atoms [O(1D)+O(3P)] is greater than unity [Φ(O)=1.20±0.15] at 193 nm indicating the presence of a channel which produces three O(3P) atoms. O2(b 1Σ) has also been detected and quantified, Φ(b 1Σ)=0.50±0.38, from O3 photolysis at 193 nm. These measurements suggest that O(1D) and O2(b1Σ) are co-produced.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 996-1003 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The quantum yields of the products, OH(X 2Π), O(3P) [plus O(1D)] and H(2S), in the photolysis of H2O2 and CH3OOH at 248 nm and 298 K have been measured. OH was directly observed by laser-induced fluorescence while the atomic species were detected by cw-resonance fluorescence. All quantum yield measurements were made using relative methods. The quantum yields of OH, O, and H in H2O2 photolysis were measured relative to the well known quantum yields of O(1D) and O(3P) in the photodissociation of O3, and H(2S) in CH3SH. The values we obtain are, 2.09±0.36, 〈0.002 and 〈0.0002 for OH, O, and H, respectively. For CH3OOH photolysis, the quantum yield of OH was measured relative to our value for OH quantum yield in H2O2 photolysis, and the quantum yields of O and H relative to those in O3 and CH3SH photodissociation, respectively. The values we obtain are, 1.00±0.18, 〈0.007 and 0.038±0.007 for OH, O, and H, respectively. In both H2O2 and CH3OOH photolysis, the observed O and H quantum yields showed an apparent dependence on the fluence of the photolysis light, the possible origin of which is discussed. The large quantum yield of OH we measure is consistent with the known continuous and unstructured absorption spectra of these molecules in this wavelength region, where the most important process is the dissociative (A˜ 1A←X˜ 1A) transition to give OH(X 2Π, v‘=0) fragment.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 447-448 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate coefficients for the reaction OH+HBr → Br+H2O have been measured at 298 K using two different experimental techniques: (1) 266 nm pulsed laser photolysis of O3/H2O/HBr/He mixtures followed by time resolved resonance fluorescence detection of OH (LFP-RF) and (2) 248 nm pulsed laser photolysis of H2O2/HBr/Ar mixtures followed by pulsed laser induced fluorescence detection of OH (LFP-LIF). In both sets of experiments, the HBr concentration was monitored in situ in the slow flow system by UV photometry. Measured rate coefficients in units of 10−12 cm3 molecule−1 s−1 are 11.4±0.3 (LFP-RF) and 10.7±0.3 (LFP-LIF) where the uncertainties are 2σ and represent precision only. The absolute accuracy of the results is estimated to be ±10%. The experimental k1 values are in good agreement with a previous LFP-RF study in our laboratory but significantly faster than values reported by several other groups.
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  • 6
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Radiation Physics and Chemistry 10 (1977), S. 183-189 
    ISSN: 0146-5724
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 136 (1987), S. 501-505 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 152 (1988), S. 507-512 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 63 (1979), S. 479-484 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Chemical Physics Letters 96 (1983), S. 129-132 
    ISSN: 0009-2614
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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