Pressure-induced phase transition in transition metal trifluorides

As a fundamental thermodynamic variable, pressure can alter the bonding patterns and drive phase transitions leading to the creation of new high-pressure phases with exotic properties that are inaccessible at ambient pressure. Using the swarm intelligence structural prediction method, the phase transition of TiF₃, from R—3c to the Pnma phase, was predicted at high pressure, accompanied by the destruction of TiF₆ octahedra and formation of TiF₈ square antiprismatic units. The Pnma phase of TiF₃, formed using the laser-heated diamond-anvil-cell technique was confirmed via high-pressure x-ray diffraction experiments. Furthermore, the in situ electrical measurements indicate that the newly found Pnma phase has a semiconducting character, which is also consistent with the electronic band structure calculations. Finally, it was shown that this pressure-induced phase transition is a general phenomenon in ScF₃, VF₃, CrF₃, and MnF₃, offering valuable insights into the high-pressure phases of transition metal trifluorides.