Infrared photofragmentation spectra of size-selected Krn+SF6 cluster ions

Abstract

Presented here are the results of an experimental study of the infrared photofragmentation patterns of size-selected Krn+SF6 cluster ions for n in the range 2⩽n⩽50. The ν3 (T1u) vibrational mode of the SF6 molecule in each cluster ion has been excited using a line-tunable CO2 infrared laser, and the subsequent fragmentation patterns were monitored for the loss of one and two krypton atoms and also for the loss of the SF6 chromophore. For ions containing more than four krypton atoms, the dominant fragmentation process observed was the loss of a single krypton atom, with the loss of SF6 being the least intense of the fragmentation channels for most clusters. For one ion, Kr3+SF6, significantly different behaviour was observed with the loss of SF6 being the dominant fragmentation route, which suggests a stable Kr3+ trimer. Fragmentation intensities were monitored as a function of laser wavelength in order to determine infrared absorption profiles for individual Krn+SF6 cluster ions. The observation of site-symmetry splittings of the triply degenerate ν3 mode and the relatively narrow linewidths suggest the presence of asymmetric, but ordered, structures. With only a maximum of three absorption features apparent for clusters consisting of less than thirty five krypton atoms, the number of structural isomers appears to be small. Comparisons are made with results previously obtained for the Arn+SF6 series of cluster ions (J. Chem. Phys., 1995, 103, 5177), and differences in spectra are attributed to the sensitivity of the SF6 molecule to its environment. Additional interpretation comes from comparisons with computer simulation studies on neutral clusters with the compositions ArnSF6 and KrnSF6 (J. Chem. Phys., 1991, 95, 6271). The appearance of SF6 loss as a minor fragmentation channel for clusters in the region of K12+SF6 is interpreted in terms of stacked structures.