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  • 1
    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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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5887-5895 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The quantum yields for OH, O(3P), O(1D), and H(2S) from the photolysis of HNO3 have been determined at 248, 222, and 193 nm at 298 K. The quantum yield for OH was observed to be near unity at 248 [Φ(OH)=0.95±0.09] and 222 nm [Φ(OH)=0.90±0.11]. However, at 193 nm the quantum yield for OH was found to be 0.33±0.06. The quantum yield for O atoms [O(3P)+O(1D)], Φ(O), was observed to be 0.031±0.010, 0.20±0.03, 0.81±0.13, at 248, 222, and 193 nm, respectively. Both O(3P) and O(1D) were observed at 222 and 193 nm, but only O(3P) was detected at 248 nm. It was observed that 40% of the O atoms formed at both 193 and 222 nm were O(1D) atoms. The upper limits for H(2S) quantum yields: Φ(H)≤0.002 at 248 nm, ≤0.01 at 222 nm, and ≤0.012 at 193 nm were also determined. This present work quantifies the photolysis channel producing HONO+O and show that it accounts for a large fraction at HNO3 photolysis at 193 nm.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5878-5886 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The primary quantum yields of OH(X 2Π),H(2S), and oxygen atoms [O(1D)+O(3P)] produced in the photodissociation of H2O2 at 193 and 222 nm have been measured at 298 K. At 193 nm, the primary quantum yields were observed to be 1.51±0.18, 0.16±0.04, and 〈0.02, for Φ(OH), Φ(H), and the sum of Φ(O) and Φ(O 1S), respectively. At 222 nm, the OH yield was Φ(OH)=2.02±0.35, the H atom yield was Φ(H)=0.024±0.012, and Φ(O) was 〈0.002. The errors quoted above are 2σ, precision plus estimated systematic errors. The OH product was directly monitored by pulsed laser-induced fluorescence, and the atomic species were detected via cw resonance fluorescence. The OH quantum yields reported here were measured relative to known product quantum yields in the dissocation of H2O2 at 248 nm. H(2S) yields were measured relative to those in photolysis of HBr and HCl, (at 193 nm) or CH3SH (at 222 nm), whereas O atoms yields were measured relative to O3 photolysis at both wavelengths. The present results indicate unit dissociation of H2O2 at both 222 and 193 nm with only two major products OH (∼80% at 193 nm, 98% at 222 nm) and H(2S) (∼20% at 193 nm, 2% at 222 nm). Up to 15% of the OH produced in the 193 nm photolysis may be vibrationally excited; however, no evidence for vibrationally excited OH was observed at 222 nm.
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