Search for precursor of pressure-induced amorphization of molecular crystal SnI4: Thermodynamic stability of low-pressure crystalline phase

The pressure–temperature phase diagram of SnI4 was investigated to examine the inherent instability of crystalline SnI4 in terms of undergoing pressure-induced solid state amorphization, by conducting molecular dynamics simulations prior to studies involving laboratory experiments. The SnI4 molecules are regarded as rigid tetrahedra interacting with one another via van der Waals forces. In order for the isothermal–isobaric ensemble to be achieved, the well-established Nosé–Klein scheme combined with the momentum scaling method was adopted when carrying out the simulations. The system was carefully heated up under fixed hydrostatic pressure from the low-pressure crystalline state across the melting point, which was determined by monitoring the time-dependence of the mean square displacement of the molecules, whereas, on cooling, the liquid state remained supercooled down to room temperature. The slope of the liquidus in the phase diagram between the low-pressure crystalline phase and the liquid phase was found to be positive, implying that the low-pressure crystalline phase has little connection with solid state amorphization. An expected overall pressure–temperature phase diagram of SnI4 is discussed.