Anisotropic exchange in ${\mathrm{LiCuVO}}_4$ probed by ESR

We investigated the paramagnetic resonance in single crystals of ${\mathrm{LiCuVO}}_4$ with special attention to the angular variation of the absorption spectrum. To explain the large resonance linewidth of the order of 1 kOe, we analyzed the anisotropic exchange interaction in the chains of edge-sharing ${\mathrm{CuO}}_6$ octahedra, taking into account the ring-exchange geometry of the nearest-neighbor coupling via two symmetric rectangular Cu-O bonds. The exchange parameters, which can be estimated from theoretical considerations, agree nicely with the parameters obtained from the angular dependence of the linewidth. The anisotropy of this magnetic ring exchange is found to be much larger than it is usually expected from conventional estimations which neglect the bonding geometry. Hence, the data yield the evidence that in copper oxides with edge-sharing structures the role of the orbital degrees of freedom is strongly enhanced. These findings establish ${\mathrm{LiCuVO}}_4$ as one-dimensional compound at high temperatures.