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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
Author(s) -
Kettle Sidney F. A.,
Diana Eliano,
Marchese Edoardo M. C.,
Boccaleri Enrico,
Stanghellini Pier Luigi
Publication year - 2011
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2944
Subject(s) - prussian blue , raman spectroscopy , chemistry , infrared , infrared spectroscopy , ion , spectral line , molecular vibration , cyanide , analytical chemistry (journal) , molecular physics , inorganic chemistry , physics , optics , electrochemistry , electrode , organic chemistry , quantum mechanics
Abstract 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 MCNM′ units arises from the axis‐specific nature of individual T 1 u modes. The interpretation of the A 1 g and E g Raman features is done in terms of localized vibrations, with involvement of additional energy terms from the lattice motions. Copyright © 2011 John Wiley & Sons, Ltd.