Volume 48, 1969

Mossbauer investigation of the intra- and inter-molecular dynamics of K3Fe(CN)6—electron-phonon instability at ∼130 K

Abstract

The Mössbauer data for K3Fe(CN)6 are analyzed in terms of inter- and intra-molecular vibrations. The characteristic Einstein temperatures obtained are θinter∼57 K and θintra∼650 K; the latter is in good agreement with i.-r. spectra. A comparison with the results for K4Fe(CN)6 and K4Fe(CN)6 . 3H2O shows that the change in the nominal valency of the central iron atom affects mainly the intermolecular vibrations. In contrast, the three water molecules (K4Fe(CN))6 . 3H2O) affect significantly the intramolecular dynamics indicating that they are bonded to CN groups forming an extended [Fe(CN)6(H2O)3]4– complex.

Thermal population of a low lying electronic energy level, due to a small rhombic distortion of the crystal field, may cause an “electron-phonon instability” which will explain the observed ln ƒ(T) anomalies as well as the reported anomalies in the thermodynamic measurements and paramagnetic susceptibilities of K3Fe(CN)6 at ∼130 K.

Article information

Article type
Paper

Discuss. Faraday Soc., 1969,48, 148-155

Mossbauer investigation of the intra- and inter-molecular dynamics of K3Fe(CN)6—electron-phonon instability at ∼130 K

Y. Hazony, Discuss. Faraday Soc., 1969, 48, 148 DOI: 10.1039/DF9694800148

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