Ferromagnetic ferroelectricity due to the Kugel-Khomskii mechanism of orbital ordering assisted by atomic Hund's second rule effects

The exchange interactions in insulators depend on the orbital state of magnetic ions, obeying certain phenomenological principles, known as Goodenough-Kanamori-Anderson rules. Particularly, the ferro order of alike orbitals tends to stabilize antiferromagnetic interactions, while the antiferro order of unlike orbitals favors ferromagnetic interactions. The Kugel-Khomskii theory provides a universal view on such coupling between spin and orbital degrees of freedom, based on the superexchange processes: namely, for a given magnetic order, the occupied orbitals tend to arrange in a way to further minimize the exchange energy. Then, if two magnetic sites are connected by the spatial inversion, the antiferro orbital order should lead to the ferromagnetic coupling break the inversion symmetry. This constitutes the basic idea of our work, which provides a pathway for designing ferromagnetic ferroelectrics: the rare but fundamentally and practically important multiferroic materials. After illustrating the basic idea on toy-model examples, we propose that such behavior can be indeed realized in the van der Waals ferromagnet <a:math xmlns:a="http://www.w3.org/1998/Math/MathML"><a:msub><a:mi>VI</a:mi><a:mn>3</a:mn></a:msub></a:math>, employing for this analysis the realistic model derived from first-principles calculations for magnetic <b:math xmlns:b="http://www.w3.org/1998/Math/MathML"><b:mrow><b:mn>3</b:mn><b:mi>d</b:mi></b:mrow></b:math> bands. We argue that the intra-atomic interactions responsible for Hund's second rule, acting against the crystal field, tend to restore the orbital degeneracy of the ionic <c:math xmlns:c="http://www.w3.org/1998/Math/MathML"><c:msup><c:mi>d</c:mi><c:mn>2</c:mn></c:msup></c:math> state in <d:math xmlns:d="http://www.w3.org/1998/Math/MathML"><d:msub><d:mi>VI</d:mi><d:mn>3</d:mn></d:msub></d:math> and, thus, provide a necessary flexibility for activating the Kugel-Khomskii mechanism of the orbital ordering. In the honeycomb lattice, this orbital ordering breaks the inversion symmetry, stabilizing the ferromagnetic-ferroelectric ground state. The symmetry breaking leads to the canting of magnetization, which can be further controlled by the magnetic field, producing a huge change of electric polarization. Published by the American Physical Society 2024