Microscopic toy model for magnetoelectric effect in polar Fe$_2$Mo$_3$O$_8$

Abstract: The kamiokite, Fe$_2$Mo$_3$O$_8$, is regarded as a promising material exhibiting giant magnetoelectric (ME) effect at the relatively high temperature $T$. Here, we explore this phenomenon on the basis of first-principles electronic structure calculations. For this purpose we construct a realistic model describing the behavior of magnetic Fe $3d$ electrons and further map it onto the isotropic spin model. Our analysis suggests two possible scenaria for Fe$_2$Mo$_3$O$_8$. The first one is based on the homogeneous charge distribution of the Fe$^{2+}$ ions amongst tetrahedral ($t$) and octahedral ($o$) sites, which tends to low the crystallographic P6$_3$mc symmetry through the formation of an orbitally ordered state. Nevertheless, the effect of the orbital ordering on interatomic exchange interactions does not seem to be strong, so that the magnetic properties can be described reasonably well by averaged interactions obeying the P6$_3$mc symmetry. The second scenario, which is supported by obtained parameters of on-site Coulomb repulsion and respects the P6$_3$mc symmetry, implies the charge disproportionation involving somewhat exotic $1+$ ionization state of the $t$-Fe sites (and $3+$ state of the $o$-Fe sites). Somewhat surprisingly, these scenarios are practically indistinguishable from the viewpoint of exchange interactions, which are practically identical in these two cases. However, the spin-dependent properties of the electric polarization are expected to be different due to the strong difference in the polarity of the Fe$^{2+}$-Fe$^{2+}$ and Fe$^{1+}$-Fe$^{3+}$ bonds. Our analysis uncovers the basic aspects of the ME effect in Fe$_2$Mo$_3$O$_8$. Nevertheless, the quantitative description should involve other ingredients, apparently related to the lattice and orbitals degrees of freedom.