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The vibrational spectra of the cyanide ligand revisited: the ν(CN) infrared and Raman spectroscopy of Prussian blue and its analogues

✍ Scribed by Sidney F. A. Kettle; Eliano Diana; Edoardo M. C. Marchese; Enrico Boccaleri; Pier Luigi Stanghellini

Publisher
John Wiley and Sons
Year
2011
Tongue
English
Weight
824 KB
Volume
42
Category
Article
ISSN
0377-0486

No coin nor oath required. For personal study only.

✦ Synopsis

A careful analysis of the

Raman spectra of the M x [M(CN) 6 ] y Prussian blue species has enabled a general model for the interpretation of the ν(CN) vibrational spectra. The spectral patterns are derived from those of the metal ions with local O h symmetry. Two limiting models are discussed. A 'localized mode' model, involving matrix-isolated species, is in much better accord with the observations than a 'factor group' model. The use of the infrared feature as fingerprint of specific M-CN-M units arises from the axis-specific nature of individual T 1u modes. The interpretation of the A 1g and E g Raman features is done in terms of localized vibrations, with involvement of additional energy terms from the lattice motions.

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