Abstract
The assignments for metal-halogen vibrations have been, for the most part, well established. In most cases it is the investigation of the metal chloride vibration that has received the most attention. Usually, the metal halide stretching vibration can be assigned unequivocally, for the frequency of the vibration will decrease as the mass of the halogen atom increases. By noting the disappearance of the stretching vibration (e.g., metal-chlorine) and the appearance of a new vibration (e.g., metal-bromine and/or metal-iodine), as one goes from the chloride to the bromide and to the iodide, accurate assignments can be made. The method is useful except when there is a change in structure in the series. Examples are known in which the central metal atom may be in an octahedral environment in the chloride and a tetrahedral environment in the bromide or iodide. This causes the coordination-number effect to counteract the mass effect, and little difference in frequency position may be noted for the metal halide vibration.1
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Ferraro, J.R. (1971). Metal Halide Vibrations. In: Low-Frequency Vibrations of Inorganic and Coordination Compounds. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-1809-5_6
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