First‐principles investigation of A‐B intersite charge transfer and correlated electrical and magnetic properties in BiCu3Fe4O12

First‐principles calculations using the augmented plane wave plus local orbitals method, as implemented in the WIEN2K code, have been carried out to study the A‐B intersite charge transfer and the correlated electrical and magnetic properties of the perovskite BiCu3Fe4O12, especially as regards the charge transfer. The results indicate that the charge transfer between A‐site Cu and B‐site Fe is by way of O 2p orbitals, and during this process orbital hybridization plays an important role. More importantly, the charge transfer is of 3d9 + 4d5L0.75→3d9L + 4d5 type (here L denotes an oxygen hole or a ligand hole). During this process, the magnetic interaction experiences a transition from Cu‐Fe ferrimagnetic coupling to G‐type antiferromagnetic coupling within B‐site Fe with paramagnetic Cu3+. As to electrical property, it undergoes a metal to insulator transition. All our calculated results are consistent with the available experimental results. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011

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