Symmetry disquisition on the TiOX phase diagram (X=Br,Cl)

The sequence of phase transitions and the symmetry of, in particular, the low temperature incommensurate and spin-Peierls phases of the quasi-one-dimensional inorganic spin-Peierls system TiOX (X=Br and Cl) have been studied using inelastic light scattering experiments. The anomalous first-order character of the transition to the spin-Peierls phase is found to be a consequence of the different symmetries of the incommensurate and spin-Peierls (P2(1)/m) phases. The pressure dependence of the lowest transition temperature strongly suggests that magnetic interchain interactions play an important role in the formation of the spin-Peierls and the incommensurate phases. Finally, a comparison of Raman data on VOCl to the TiOX spectra shows that the high energy scattering previously observed has a phononic origin.