Multiphoton Dissociation and Thermal Unimolecular Reactions Induced by Infrared Lasers. [REAMPA Code].

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  • Release Date : 1981
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  • File Size : 53,53 MB
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Multiphoton Dissociation and Thermal Unimolecular Reactions Induced by Infrared Lasers. [REAMPA Code]. by PDF Summary

Book Description: Multiphoton dissociation (MPD) of ethyl chloride was studied using a tunable 3.3 .mu.m laser to excite CH stretches. The absorbed energy increases almost linearly with fluence, while for 10 .mu.m excitation there is substantial saturation. Much higher dissociation yields were observed for 3.3 .mu.m excitation than for 10 .mu.m excitation, reflecting bottlenecking in the discrete region of 10 .mu.m excitation. The resonant nature of the excitation allows the rate equations description for transitions in the quasicontinuum and continuum to be extended to the discrete levels. Absorption cross sections are estimated from ordinary ir spectra. A set of cross sections which is constant or slowly decreasing with increasing vibrational excitation gives good fits to both absorption and dissociation yield data. The rate equations model was also used to quantitatively calculate the pressure dependence of the MPD yield of SF6 caused by vibrational self-quenching. Between 1000-3000 cm−1 of energy is removed from SF6 excited to approx.> 60 kcal/mole by collision with a cold SF6 molecule at gas kinetic rate. Calculation showed the fluence dependence of dissociation varies strongly with the gas pressure. Infrared multiphoton excitation was applied to study thermal unimolecular reactions. With SiF4 as absorbing gas for the CO2 laser pulse, transient high temperature pulses were generated in a gas mixture. IR fluorescence from the medium reflected the decay of the temperature. The activation energy and the preexponential factor of the reactant dissociation were obtained from a phenomenological model calculation. Results are presented in detail. (WHK).

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