We report high-pressure x-ray diffraction and magnetization measurements combined with ab-initio calculations to demonstrate that the high-pressure optical and transport transitions recently reported in TiOCl, correspond in fact to an enhanced Ti3+-T
i3+ dimerization existing already at room temperature. Our results confirm the formation of a metal-metal bond between Ti3+ ions along the b-axis of TiOCl, accompanied by a strong reduction of the electronic gap. The evolution of the dimerization with pressure suggests a crossover from the spin-Peierls to a conventional Peierls situation at high pressures.
