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V. N. Lokhman, D. D. Ogurok, E. A. Ryabov, V. S. Letokhov

IR Multiple-Photon + UV Mutliphoton Laser Selective Fragmentation and Ionization of SF₆ and CF₂HCl Molecules

We have studied the formation mechanisms of the S⁺ and SF⁺ and also CF⁺ ions resulting from the multiple-photon IR + UV excitation of the SF₆ and CF₂HCl molecules, respectively. It is demonstrated that in SF₆ exist at least two ion formation channels. The first is the UV multiphoton fragmentation and ionization of the SF₅ radicals formed in the course of the IR MP dissociation of SF₆. The second starts with the UV excitation of the highly vibrationally excited SF₆ molecules themselves. As for the IR + UV irradiation of CF₂HCl, the experiments performed allow us to conclude that the CF⁺ ions observed are produced in the course of the UV multiphoton excitation of the CF₂ radicals, followed by their fragmentation and ionization, the radicals themselves being formed as a result of the IR MPD of CF₂HCl. This effect has been used to study the unimolecular decay kinetics of CF₂HCl, as well as the kinetics of the isotopic selectivity of the IR MPD process under molecular beam conditions.

Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag

Print ISSN: 0942-9352
Volume: 215, 12/2001
Pages: 1469

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