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  • 1
    Electronic Resource
    Electronic Resource
    Decomposition of highly vibrationally excited CDCl3 (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5191-5197 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Decomposition of highly vibrationally excited CDCl3 was studied in the time domain by measuring laser-induced fluorescence from one of the decomposition products CCl2 or by observing luminescence from CCl2 radical fragments produced in the A˜(1B1) state following IR excitation. It is shown that highly vibrationally excited CDCl3 can be made via two different routes: i(Slashthrough accent mark)mple optical absorption of an incident 13CO2 laser pulse or through collision-moderated energy pooling coupled with photon absorption. Higher fluence measurements are consistent with the former and support previous claims that the infrared multiphoton decomposition probability for CDCl3 is pressure independent. At a lower fluence the vibrational up-pumping mechanism apparently relies heavily upon collisions, which supports other claims that the decomposition probability is pressure dependent. The results of the present work reconcile these previous disparate claims. Furthermore, there is an indication that the vibrational energy transferred during a collision could be much larger than collision-induced dipole selection rules would allow. In some of the experiments, electronically excited CCl2 fragments are created but only through post-laser-pulse collisions that appear to involve exchanges of very large amounts of vibrational energy. By contrast, no electronically excited CCl2 is produced following excitation with the CO2 laser alone. The experiments also corroborate an earlier prediction that the extent of reaction is governed by adiabatic expansion of the centrally heated zone, even at pressures as low as 0.66 kPa, rather than by diffusion, as is commonly believed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462759
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  • 2
    Electronic Resource
    Electronic Resource
    Evaluation of the collisionless contribution to the measured infrared multiphoton decomposition (1992)
    Springer
    Applied physics 55 (1992), S. 341-346 
    Details
    ISSN: 1432-0649
    Keywords: 82.20.Wt ; 33.80.Wz ; 42.60.If
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Some of the problems associated with modelling infrared multiphoton decomposition of gaseous molecules are presented. As an example, the cumulative log normal distribution function model is presented in an experimental context where the effects of laser beam geometry and molecular collisions have been taken into account. It is argued that any laser radial profile other than Gaussian, including “tophat”, can unnecessarily complicate the testing of a model and should be used with caution.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00333078
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  • 3
    Electronic Resource
    Electronic Resource
    Two-color multiphoton decomposition of 1-bromo 2-fluoroethaneWe are pleased to make this contribution in memory of Bob Back. Bob collaborated with our group at Chalk River on many projects over the last decade. He was a friend, colleague, and teacher to us and we have felt his absence on many occasions, not the least of which was while writing this article. We often asked one another, “How would Bob have explained the results?” Needless to say, Bob will continue to be missed. (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 147-158 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multiphoton decomposition of 1-bromo 2-fluoroethane (CH2BrCH2F, BFE) with a two-color CO2 infrared laser is reported as a function of number of laser pulses. For single color irradiation at a wavelength chosen to excite BFE, the decomposition product, vinyl fluoride, which accumulates during the many-pulse MPD experiment, is found to deactivate BFE decomposition. When a second laser, tuned to a vinyl fluoride absorption is introduced, coincident with the first, the vinyl fluoride is found to activate further BFE decomposition. These results are accounted for in terms of a pressure-dependent model. Changes in model parameters, upon addition of the second laser, are shown to be consistent with interpretations in terms of collision-dependent reaction schemes. © 1994 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260115
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