RESUMEN
A molecular crystalline SnI4undergoes pressure-induced solid-state amorphization via molecular dissociation to the high-density amorphous (HDA) state, which we call Am-I. In the present study, we examine the reverse transition process from Am-I to the low-density amorphous (LDA) state, called Am-II. We first measure the structure factor on decompression from 30 GPa down to 1.1 GPa at room temperature, usingin situangle-dispersive synchrotron x-ray measurement and a diamond anvil cell. We then estimate the density, which exhibits an abrupt change between 3.3 and 3.0 GPa, indicating the HDA(Am-I)-to-LDA(Am-II) transition. We use the density and the molecular configuration generated from a molecular dynamics simulation as input to a reverse Monte Carlo fit. The fit vividly visualizes gradual molecular reassociation between 18 and 14 GPa within the Am-I region. The Am-I state can thus be divided into two states: the high-pressure Am-I state containing isolated Sn atoms and the low-pressure Am-I state consisting of deformed molecules connected by metallic I2bonds. In the latter state, the molecular shape becomesC3v-like just before the transition to Am-II, in which molecules recover the originalTdsymmetry. This local symmetry change has been detected on the liquid-liquid transition of SnI4, suggesting the strong coupling between the local symmetry and the global order parameter of density.
RESUMEN
A SnI4 molecule lowers its symmetry from T d to [Formula: see text] on the liquid-liquid transition. Because it is possible to lower the molecular symmetry without violating the crystalline symmetry, it is worth examining whether the deformation occurs in the crystalline phase field. Extended x-ray absorption fine structure (EXAFS) measurements on the crystalline state were carried out to investigate the change in the environment around a Sn atom at high pressures and temperatures. We could not find clear evidence on the symmetry change of molecules even close to the melting points, where the melting curve becomes abnormally flat against pressure. Indeed, no inconsistency was found when we assumed that the coordination number of a Sn atom remains unchanged in the temperature and pressure range examined. The situation remains true when the system entered the high-pressure crystalline phase on compression. We can propose a consistent scenario as to the structural change on the phase transformation. The incompressibility of a SnI4 molecule could be suitably quantified. The procedure enabled us to conclude the molecule is more than an order of magnitude incompressible than the lattice.
RESUMEN
The location of the liquidus in the low-pressure crystalline phase of SnI(4) was determined utilizing in situ x-ray diffraction measurements under pressures up to approximately 3.5 GPa. The liquidus is not well fitted to a monotonically increasing curve such as Simon's equation, but breaks near 1.5 GPa and then becomes almost flat. The results are compared to those from molecular dynamics simulations. Ways to improve the model potential adopted in the simulations are discussed.
