Orthorhombic distortion and orbital order in the vanadium spinel FeV2O4.

Using synchrotron and neutron diffraction measurements, we find a low-temperature orthorhombic phase in vanadium spinel FeV2O4. The orbital order of V3+ ions with tetragonal normal modes occurs at 68 K, and this leads to an appearance of the pseudotetragonal phase at a noncollinear ferrimagnetic transition temperature. Below the magnetic transition temperature, unconventional behavior of the orbital state of Fe2+ ions accompanied by the emergence of the orthorhombic phase was observed by using the normal mode analysis. We have also studied the structural properties of orbitally diluted materials. The orthorhombic phase, which is significantly affected by the other ions, is intrinsic in FeV2O4. We suggest the orthorhombic phase is strongly related with the double orbital states of Fe2+ and V3+ ions.