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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 SF 6  and CF 2 HCl molecules, respectively. It is demonstrated that in SF 6  exist at least two ion formation channels. The first is the UV multiphoton fragmentation and ionization of the SF 5  radicals formed in the course of the IR MP dissociation of SF 6 . The second starts with the UV excitation of the highly vibrationally excited SF 6  molecules themselves. As for the IR + UV irradiation of CF 2 HCl, the experiments performed allow us to conclude that the CF +  ions observed are produced in the course of the UV multiphoton excitation of the CF 2  radicals, followed by their fragmentation and ionization, the radicals themselves being formed as a result of the IR MPD of CF 2 HCl. This effect has been used to study the unimolecular decay kinetics of CF 2 HCl, as well as the kinetics of the isotopic selectivity of the IR MPD process under molecular beam conditions.

IR Multiple-Photon + UV Mutliphoton Laser Selective Fragmentation and Ionization of SF 6 and CF 2 HCl Molecules