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

Literature Information

Publication Date 2014-04-03
DOI 10.1039/C4CP00662C
Impact Factor 3.676
Authors

Tim Krah, Nadia Ben Amor, Vincent Robert


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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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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