Orbital dimerization in NaTiSi2O6: An orbital analogue of the spin-Peierls phase transition

We measure the Raman scattering spectra of NaTiSi2O6, analyze the vibrational properties, and study the origin of the phase transition in this compound. In this quasi-one-dimensional S = 1/2 system we observe anomalous high-temperature phonon broadenings, and large changes of the phonon energies and line-widths across the phase transition temperature of 210 K. These results, combined with theoretical considerations, indicate that the phonon anomalies originate from an orbital order-disorder type of phase transition. We find that the high temperature dynamical Jahn-Teller phase of NaTiSi2O6 exhibits a spontaneous breaking of translational symmetry into a dimerized, Jahn-Teller distorted, orbital ordered state under the formation of spin valence bonds.