Raman evidence for dimerization and Mott collapse in α-RuCl₃ under pressures

We perform Raman spectroscopy studies on $\alpha$-RuCl$_3$ at room temperature to explore its phase transitions of magnetism and chemical bonding under pressures. The Raman measurements resolve two critical pressures, about $p_1=1.1$~GPa and $p_2=1.7$~GPa, involving very different intertwining behaviors between the structural and magnetic excitations. With increasing pressures, a stacking order phase transition of $\alpha$-RuCl$_3$ layers develops at $p_1=1.1$~GPa, indicated by the new Raman phonon modes and the modest Raman magnetic susceptibility adjustment. The abnormal softening and splitting of the Ru in-plane Raman mode provide direct evidence of the in-plane dimerization of the Ru-Ru bonds at $p_2=1.7$~GPa. The Raman susceptibility is greatly enhanced with pressure increasing and sharply suppressed after the dimerization. We propose that the system undergoes Mott collapse at $p_2=1.7$~GPa and turns into a dimerized correlated band insulator. Our studies demonstrate competitions between Kitaev physics, magnetism, and chemical bondings in Kitaev compounds.