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2012 | OriginalPaper | Chapter

21. Vibronic Approach to the Cooperative Spin Transitions in Crystals Based on Cyano-Bridged Pentanuclear M2Fe3 (M=Co, Os) Clusters

Authors : Serghei Ostrovsky, Andrew Palii, Sophia Klokishner, Michael Shatruk, Kristen Funck, Catalina Achim, Kim R. Dunbar, Boris Tsukerblat

Published in: Vibronic Interactions and the Jahn-Teller Effect

Publisher: Springer Netherlands

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Abstract

In this article we present a theoretical microscopic approach to the problem of cooperative spin crossover in crystals based on cyano-bridged pentanuclear metal clusters \(\{{[{\mathrm{M(CN)}}_{6}]}_{2}{[{\mathrm{Fe(tmphen)}}_{2}]}_{3}\}\) (M = Co, Os) with a trigonal bipyramidal structure. The low-spin to high-spin transition is considered as a cooperative phenomenon that is driven by the interaction of the electronic shells of the Fe ions with the full symmetric deformation of the local surrounding that is extended over the crystal lattice via the acoustic phonon field. Due to the proximity of Fe ions within the metal cluster, the short-range intracluster interactions between these ions via the optic phonon field is included as well. The interrelation between short- and long-range phonon induced interactions between metal ions was shown to determine the type and the temperature of spin transition in cluster systems. The proposed model is applied to the systems with temperature induced spin transition within the single metal ion as well as to the complexes with spin transition caused by the charge transfer between different ions in the cluster. A wide set of the experimental data on the temperature dependence of the magnetic susceptibility and Mössbauer spectra is interpreted qualitatively and quantitatively. The approach described in this paper represents a theoretical tool for the study of spin-crossover systems based on metal clusters as structural units of the crystal lattice.

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Metadata
Title
Vibronic Approach to the Cooperative Spin Transitions in Crystals Based on Cyano-Bridged Pentanuclear M2Fe3 (M=Co, Os) Clusters
Authors
Serghei Ostrovsky
Andrew Palii
Sophia Klokishner
Michael Shatruk
Kristen Funck
Catalina Achim
Kim R. Dunbar
Boris Tsukerblat
Copyright Year
2012
Publisher
Springer Netherlands
DOI
https://doi.org/10.1007/978-94-007-2384-9_21

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