Recent state-of-the-art crystallographic investigations of transition metal spinel compounds have revealed that the d-orbital charge carriers undergo ordering transitions with the formation of local 'molecular bonding' units such as dimers in MgTi2O4, octomers in CuIr2S 4, and heptamers in AlV2O4. Herein, we provide a unifying scheme involving one-dimensional (1D) orbital wave (OW) ordering applicable to all of these spinels. The relative phase of the orbitals in the chains is shown to be crucial to the formation of different local units, and thus both the amplitude and phase of the OW play important roles. Examination of Horibe et al's (2006 Phys. Rev. Lett. 96 086406) structure for AlV 2O4 serves as the vehicle for developing the general behaviour for such orbital wave ordering. Ordered AlV2O4 will be seen to organize into three equivalent chains in 2D Kagome planes coupled so as to form units of three dimer bonds. Three additional equivalent chains manifest a more complex tetramerization with three different charge states and two different bonding schemes. The OW ordering scheme developed is extended to other spinel and related compounds with local triangular transition metal coordination and partial filling of the t2g-d orbitals.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)