Abstract
The optical spectra of IrCl62− in single crystals of Cs2ZrCl6, Cs2HfCl6, and K2SnCl6 have been studied at helium temperature. Both molecular-orbital theory and ligand-field theory are used to interpret the results. The rich vibrational structure observed is analyzed in terms of the vibrational modes of the IrCl62− complex. Several long progressions involving up to five quanta of the completely symmetric vibration, γ1g, are observed throughout the spectrum, indicating that the transitions are to states in which the Ir–Cl bond length has been changed.

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