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 Pc from a Mott-insulator to a metallic phase in the ab plane with a strong Ti-Ti dimerization along b. At a pressure Pc′>Pc 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 Pc 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 t2g 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.
ASJC Scopus subject areas
- Physics and Astronomy(all)