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  • 1
    Electronic Resource
    Electronic Resource
    Energy dependence of infrared emission from azulene C–H stretching vibrations (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 6211-6218 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: New data are described on the energy dependence of infrared fluorescence (IRF) from the C–H stretch modes (∼3050 cm−1) of vibrationally excited azulene (C10H8). An optoacoustic method was used to measure the absorbed laser energy and determine the number of excited molecules, while time-resolved infrared emission was recorded. The experimental uncertainties of ∼5% are much smaller than in previous work and the agreement between the experiments and the theory for the IRF intensity is excellent for total vibrational energies from 14 000 to 33 000 cm−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454459
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  • 2
    Electronic Resource
    Electronic Resource
    Energy-dependent collisional deactivation of vibrationally excited azulene (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 6219-6227 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Collisional energy transfer parameters for highly vibrationally excited azulene have been deduced from new infrared fluorescence (IRF) emission lifetime data with an improved calibration relating IRF intensity to vibrational energy [J. Shi, D. Bernfeld, and J. R. Barker, J. Chem. Phys. 88, 6211 (1988), preceding paper]. In addition, data from previous experiments [M. J. Rossi, J. R. Pladziewicz, and J. R. Barker, J. Chem. Phys. 78, 6695 (1983)] have been reanalyzed based on the improved calibration. Inversion of the IRF decay curves produced plots of energy decay, which were analyzed to determine 〈ΔE〉, the average energy transferred per collision. Master equation simulations reproduced both the original IRF decays and the deduced energy decays. A third (simple) method of 〈ΔE〉 determination agrees well with the other two. The results show 〈ΔE〉 to be nearly directly proportional to the vibrational energy of the excited azulene from ∼8000 to 33 000 cm−1. At high energies, there are indications that the 〈ΔE〉 energy dependence may be slightly reduced.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454460
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  • 3
    Electronic Resource
    Electronic Resource
    FTIR product study of the chlorine-initiated oxidation of chloroethane: reactions of the alkoxy radical CH3CHClO (1993)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 6184-6192 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100125a016
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  • 4
    Electronic Resource
    Electronic Resource
    Evidence for the three-center elimination of hydrogen chloride from 1-chloroethoxy (1993)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 9686-9694 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100140a027
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  • 5
    Electronic Resource
    Electronic Resource
    Reaction of Chlorine Atoms with Methylperoxy and Ethylperoxy Radicals (1994)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 2083-2089 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100059a017
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  • 6
    Electronic Resource
    Electronic Resource
    Emission from ozone excited electronic states (1990)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 94 (1990), S. 8390-8393 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100385a004
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  • 7
    Electronic Resource
    Electronic Resource
    Incubation in cyclohexene decomposition at high temperatures (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 187-206 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed master equation simulation has been carried out for the thermal unimolecular decomposition of C6H10 in a shock tube. At the highest temperatures studied experimentally [J. H. Kiefer and J. N. Shah, J. Phys. Chem., 91, 3024 (1987)], the average thermal vibrational energy is greater than the reaction threshold and therefore 〈ΔE〉 (up and down steps) is positive for molecules at that energy, rather than negative; the converse is true at lower temperatures. The calculated incubation time, in which the decomposition rate constant rises to 1/e of its steady state value, is found to be only weakly dependent on temperature (at constant pressure) between 1500 K and 2000 K and to depend almost exclusively on 〈ΔE〉d (down steps, only), and not on collision probability model. Simulations of the experimental data show the magnitude of 〈ΔE〉d depends weakly on assumed collision probability model, but is nearly independent of temperature. The second moment 〈ΔE〉½ is found to be independent of both temperature and transition probability model. The experimental data are not very sensitive to the possible energy-dependence of 〈ΔE〉d for a wide range of assumptions. It is concluded that the observed experimental “delay times” probably can be identified with the incubation time; further experiments are desirable to test this possibility and obtain more direct measures of the incubation time.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220207
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetic studies of the deactivation of O2(1Σg+) and O(1D) (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1283-1301 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the deactivation of O2(1Σg+) is studied in real time. O2(1Σg+) is generated in this system by the O(1D) + O2 reaction following O3laser flash photolysis in the presence of excess O2, and it is monitored by its characteristic emission band at 762 nm. Quenching rate constants were obtained for O2, O3, N2, CO2, H2O, CF4and the rare gases. Since O(1D) is the precursor for the formation of O2(1Σg+), the addition of an O(1D) quencher effectively lowers the initial concentration of O2(1Σg+). By measuring the initial intensity of the 762 nm fluorescence signal, the relative quenching efficiencies were determined for O(1D) quenching by N2, CO2, Xe, and Kr with respect to O2; the results are in good agreement with literature values.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550221207
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  • 9
    Electronic Resource
    Electronic Resource
    A kinetic study of the reaction of fluorine atoms with CH3F, CH3Cl, CH3Br, CF2H2, CO, CF3H, CF3CHCl2, CF3CH2F, CHF2CHF2, CF2ClCH3, CHF2CH3, and CF3CF2H at 295 ± 2 K (1993)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 651-665 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A variety of relative and absolute techniques have been used to measure the reactivity of fluorine atoms with a series of halogenated organic compounds and CO. The following rate constants were derived, in units of cm3 molecule-1 s-1: CH3F, (3.7 ± 0.8) × 10-11, CH3Cl, (3.3 ± 0.7) × 10-11; CH3Br, (3.0 ± 0.7) × 10-11; CF2H2, (4.3 ± 0.9) × 10-12; CO, (5.5 ± 1.0) × 10-13 (in 700 torr total pressure of N2 diluent); CF3H, (1.4 ± 0.4) × 10-13; CF3CCl2H (HCFC-123), (1.2 ± 0.4) × 10-12; CF3CFH2 (HFC-134a), (1.3 ± 0.3) × 10-12, CHF2CHF2 (HFC-134), (1.0 ± 0.3) × 10-12; CF2ClCH3 (HCFC-42b), (3.9 ± 0.9) × 10-12, CF2HCH3 (HFC-152a), (1.7 ± 0.4) × 10-11; and CF3CF2H (HFC-125), (3.5 ± 0.8) × 10-13. Quoted errors are statistical uncertainties (2σ). For rate constants derived using relative rate techniques, an additional uncertainty has been added to account for potential systematic errors in the reference rate constants used. Experiments were performed at 295 ± 2 K. Results are discussed with respect to the previous literature data and to the interpretation of laboratory studies of the atmospheric chemistry of HCFCs and HFCs. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550250806
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetic studies of Cl-atom reactions with selected aromatic compounds using the photochemical reactor-FTIR spectroscopy technique (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 349-358 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constant measurements have been carried out on the Cl-atom reactions with benzene, chlorobenzene, toluene, xylene, and styrene in 740 torr of air at room temperature (295 K), using the photochemical reactor-FTIR spectroscopy technique. The Cl atoms were generated by the UV photolysis of Cl2, and the reference compounds were CHF, Cl for benzene and chlorobenzene and isobutane for toluene xylene and styrene. Using the absolute rate constant for these two reference compounds reported in the literature, the following kinetic data were obtained for the study compounds (in units of cm3s-1). \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{ll} {\rm Benzene} & (1.3\pm 0.3)\times 10 ^{-15}\\ {\rm Chlorobenzen} & (9.8\pm 2.4)\times 10 ^{-16}\\ {\rm Toluene} & (5.9\pm 0.5)\times 10 ^{-11}\\ o-{\rm Xylene} & (1.5\pm 0.1)\times 10 ^{-10}\\ m-{\rm Xylene} & (1.4\pm 0.1)\times 10 ^{-10}\\ p-{\rm Xylene} & (1.5\pm 0.1)\times 10 ^{-10}\\ {\rm Styrene} & (3.6\pm 0.3)\times 10 ^{-10}\end{array} $$\end{document} The quoted error bars are for ± 2σ. The present kinetic results are compared with available literature data to update and expand the kinetics database for Cl-atom reactions of organic compounds. The results are also analyzed to provide insights into the reaction mechanism for the Cl-atom initiated oxidation of benzene under atmospheric conditions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 349-358, 1997
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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