High Pressure Structure and Decomposition of MoS$_{2}$

Abstract: The high pressure structural and electronic evolution of bulk MoS$_2$, an important transition metal layered dichalchogenide, is currently under active investigation. Recent theoretical and experimental work predicted and verified a 2H$_c \to$ 2H$_a$ layer sliding structural transition at 20 GPa and a band overlap semiconductor-semimetal transition in the same pressure range. The 2H$_a$ structure is known to persist up to pressure of 81 GPa but properties at higher pressures remain experimentally unknown. Here we predict, with a reliable first-principles evolutionary search, that major structural transformations should take place in equilibrium at higher pressures near 130-140 GPa. The main motif is a decomposition into MoS + S, also heralded in a small bimolecular cell by the appearance of a metastable non-layered metallic MoS$_2$ structure with space group \textit{P4/mmm}. Unlike semimetallic 2H$_a$-MoS$_2$, both this phase and sulphur in the fully phase separated system are fully metallic and superconducting with higher critical temperatures than alkali-intercalated MoS$_2$.