Abstract
Abstract The mechanism whereby the S + and SF + ions are formed as a result of the combined IR + UV irradiation of jet-cooled SF 6 molecules is studied both experimentally and theoretically. It is demonstrated that there exist at least two channels for these ions to form. The first is the UV multiphoton fragmentation and ionization of the SF 5 radicals formed in the course of the IR multiple-photon (MP) dissociation of the SF 6 molecules. The second starts with the UV excitation of the highly vibrationally excited SF 6 molecules formed during IR MP excitation. A theoretical model of the process is developed, describing in particular the dynamics of the IR MP excitation and dissociation of the SF 6 molecules and the subsequent space–time evolution of the products. This model is used to find the efficiency of the UV MP ionization of SF 6 molecules as a function of their vibrational energy. At λ =232 nm this process starts with the SF 6 molecules having a vibrational energy of E vib ≳ (15–20)×10 3 cm −1 .
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