Orientational ordering, site structure, and dynamics for octahedral molecules in low temperature matrices: SF6 and SeF6 in rare gas solids

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Abstract
From polarization studies of high resolution IR spectra of SF6 and SeF6 trapped in noble gas solids we show that much of the structure observed for the stretching mode represents site symmetry split components for low symmetry trapping sites, the triply‐degenerate ν3 mode being split into a doubly‐ and singly‐degenerate mode. Most of the sites showing polarization are orientationally ordered with the singly‐degenerate component perpendicular to the substrate. We attribute the driving force for ordering to guest–host interaction potentials which result in registry between the molecules and the (111) growth plane during deposition. The observed orientational ordering combined with high temperature annealing studies has allowed the identification of the symmetry of certain trapping sites and further analysis of vibrational dephasing dynamics. Several sites with the same nominal symmetry and structure can be tracked through the matrices discussed herein. The implications of the ordering of impurity structure in a host lattice formed by vapor deposition are discussed.