Switching magnetic interactions in the NiFe Prussian Blue Analogue: an ab initioinspection

The magnetic interaction in the Ni(ii)-Fe(iii) Prussian Blue Analogue is investigated by means of Difference Dedicated Configuration Interaction (DDCI) calculations. Embedded cluster calculations are performed to extract the exchange coupling constant Jwith respect to an opening of the Ni-NC-Fe brid...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2014-04, Vol.16 (20), p.9509-9514
Main Authors: Krah, Tim, Amor, Nadia Ben, Robert, Vincent
Format: Article
Language:English
Subjects:
Analogue
Cations
Electron transfer
Ferromagnetism
Iron compounds
Mathematical analysis
Networks
Nickel
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Summary:The magnetic interaction in the Ni(ii)-Fe(iii) Prussian Blue Analogue is investigated by means of Difference Dedicated Configuration Interaction (DDCI) calculations. Embedded cluster calculations are performed to extract the exchange coupling constant Jwith respect to an opening of the Ni-NC-Fe bridge while maintaining a rigid Fe(CN) sub(6) unit. It is shown that such active distortion significantly modifies the magnetic interaction scheme in the material. Not only a ferromagnetic to antiferromagnetic transition is observed, but the Jvalue is varied from +11.4 cm super(-1) to -12.5 cm super(-1) when the Ni-Fe cyanide bridge is opened by 20 degree . The enhancement of the intersite hopping electron transfer integral by a factor of 1.5 can be correlated with the observed Na super(+)-ion mobility in a unified "cation-coupled electron transfer" (CCET) process. These results stress the complexity and originality of this class of compounds evidenced by the versatility of their magnetic network.
ISSN:1463-9076
1463-9084
DOI:10.1039/c4cp00662c