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Updated: May 1, 2026

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Switching magnetic interactions in the NiFe Prussian Blue Analogue: an ab initio inspection
Tim Krah1, Nadia Ben Amor, Vincent Robert
1Laboratoire de Chimie Quantique, Université de Strasbourg, 1 Rue Blaise Pascal, 67000 Strasbourg, France. tim.krah@etu.unistra.fr vrobert@unistra.fr.
Abstract:
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 J with respect to an opening of the Ni-NC-Fe bridge while maintaining a rigid Fe(CN)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 J value is varied from +11.4 cm(-1) to -12.5 cm(-1) when the Ni-Fe cyanide bridge is opened by 20°. The enhancement of the intersite hopping electron transfer integral by a factor of 1.5 can be correlated with the observed Na(+)-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.
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