Study of the pressure effects in TiOCl by ab initio calculations

Electronic structure calculations on the low-dimensional spin-1/2 compound TiOCl were performed at several pressures in the orthorhombic phase, finding that the structure is quasi-one-dimensional. The Ti3+ (d1) ions have one t2g orbital occupied (dyz) with a large hopping integral along the b-direction of the crystal. The most important magnetic coupling is Ti-Ti along the b-axis. The transition temperature (Tc) has a linear evolution with pressure, and at about to 10 GPa this Tc is close to room temperature, leading to a room temperature spin-Peierls insulator-insulator transition, with an important reduction of the charge gap in agreement with the experiment. On the high-pressure monoclinic phase, TiOCl presents two possible dimerized structures with a long or short dimerization. Long dimerized state occurs above 15 GPa, and below this pressure the short dimerized structure is the more stable phase.