Orbital order in the low-dimensional quantum spin system TiOCl probed by ESR -: art. no. 140405

We present electron-spin-resonance data of Ti3+ (3d(1)) ions in single crystals of the novel layered quantum spin magnet TiOCl. The analysis of the g tensor yields direct evidence that the d(xy) orbital from the t(2g) set is predominantly occupied and owing to the occurrence of orbital order a linear spin chain forms along the crystallographic b axis. This result corroborates recent theoretical local-density approximation + U calculations of the band structure. The temperature dependence of the parameters of the resonance signal suggests a strong coupling between spin and lattice degrees of freedom and gives evidence for a transition to a nonmagnetic ground state at 67 K.