Using Car-Parrinello molecular dynamics we investigate the behavior of the low-dimensional multiorbital Mott insulator TiOCl under pressure. We show that the system undergoes two consecutive phase transitions, first at $P_c$ from a Mott-insulator to a metallic phase in the $ab$ plane with a strong Ti-Ti dimerization along $b$. At a pressure $P_c^{\prime }>P_c$ the dimerization disappears and the system behaves as a uniform metal. This second transition has not yet been reported experimentally. We show that the insulator-to-metal transition at $P_c$ is driven by the widening of the bandwidth rather than structural changes or reduction of crystal field splittings and it shows a redistribution of the electronic occupation within the $t_{2g}$ bands. Our computed pressure-dependent lattice parameters are consistent with experimental observations and the existing controversy on the change of crystal symmetry at high pressures is discussed.

• Received 13 July 2008

DOI:https://doi.org/10.1103/PhysRevLett.101.136406