Infrared photofragmentation spectra of size-selected SF6⋅Ar+n cluster ions

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Abstract
Results are presented of a detailed experimental study of the infrared photofragmentation patterns of size‐selected SF6⋅Ar+n cluster ions for n in the range 3 to 70. Line‐tuneable CO2 and N2O lasers have been used to excited the ν3 vibrational mode of the SF6 molecule which is followed by the loss of one and two argon atoms as the principal fragmentation routes. Which of the two processes is dominant depends quite strongly on the size of the cluster ion concerned, with very pronounced fluctuations in the relative intensities of photofragments being observed for cluster ions in the range SF6⋅Ar+3 to SF6⋅Ar+25. Only for SF6⋅Ar+3 is the fragmentation pattern markedly different from that found for the other ions; an observation that supports an earlier conclusion regarding the relative ionisation energies of the two constituents [Stace et al. J. Phys. Chem. 97, 11363 (1993)]. A summation of fragment ion intensities as a function of laser wavelength is used to determine infrared absorption profiles and these have been recorded for individual clusters containing up to 70 argon atoms. Clusters containing fewer than 40 argon atoms appear to form single structures, with both the absorption profile shapes and selected hole‐burning experiments suggesting that the number of isomers is small. The presence of isomers only appears to become significant when the clusters contain more than 40 argon atoms. The observation of site splittings for the triply degenerate ν3 vibrational mode of SF6, together with the comparatively narrow linewidths seen for clusters containing between 15 and 40 rare gas atoms, indicates the presence of ordered structures. Such a conclusion implies that the clusters are solidlike rather than liquidlike. Overall, the results demonstrate that there is a clear correlation between those criteria previously used to identify the presence of stable cluster ion structures, i.e., mass spectra and unimolecular fragmentation patterns, and the corresponding infrared fragmentation patterns and absorption profiles. Of the ions studied, SF6⋅Ar+21 stands out as being particularly stable and worthy of future theoretical attention.