Pressure-induced local symmetry breaking upon liquid-liquid transition of GeI4 and SnI4.

SnI4 and GeI4 have been confirmed to have another liquid state appearing on compression. To identify the microscopic pathway from the low- to high-pressure liquid states, the structure of these liquids in the appropriate thermodynamic regions was analyzed using a reverse Monte Carlo method. The occurrence of pressure-induced symmetry lowering of molecules, from regular tetrahedral to ammonia-like pyramidal symmetry, was then recognizable in these systems. This symmetry lowering is reflected in the change in shape of the molecular form factor. The latter change occurs abruptly near the expected transition pressure in liquid SnI4, whereas it proceeds gradually in GeI4. This is consistent with our observation that SnI4 seems to undergo a first-order liquid-liquid transition, whereas the transition seems to end up with a crossover in liquid GeI4. Interestingly, when the molecular density becomes high, it is possible for the two-body intermolecular interaction to have a double-minimum character, which offers two characteristic length scales corresponding to two liquid states with different densities. However, quantum chemical calculations show that molecular deformation for this type of symmetry lowering results in an increase in electronic energy, which leaves the problem of the physical origin for this anisotropic deformation. We speculate that this symmetry lowering occurs as a precursor to the whole change in the liquid structure.

A polymerization scenario of the liquid-liquid transition of GeI4.

SnI4 and GeI4 have been shown to exhibit similar polyamorphic nature. We examine the microscopic nature of the liquid-liquid transition in GeI4 by conducting an isothermal-isobaric molecular dynamics simulation for the system composed of rigid tetrahedral molecules. The model allows us to semiquantitatively discuss the structural properties of liquid GeI4 below 1 GPa. We define a physical bond between the nearest intermolecular iodine sites satisfying the conditions of forming the metallic I2 bond. We then focus on the formation of molecular clusters in dynamic networks of the bonds. The clusters are mainly formed by molecules whose nearest pairs are in edge-to-edge, face-to-edge, and vertex-to-edge orientations. The clusters grow as pressure increases, and the onset of percolation is observed below 1 GPa. The finite-size scaling analysis for the percolation probability identifies that the threshold pressure is [Formula: see text] GPa for the present model, which is near the extension of the boundary between the two liquid phases. We thus speculate that the liquid-liquid transition of GeI4 is attained by polymerization, i.e. percolation of molecular networks. The same percolation scenario with a slight modification such as introducing a bootstrap mechanism is expected to apply to the transition in liquid SnI4.

Does a network structure exist in molecular liquid SnI4 and GeI4?

The existence of a network structure consisting of electrically neutral tetrahedral molecules in liquid SnI4 and GeI4 at ambient pressure was examined. The liquid structures employed for the examination were obtained from a reverse Monte Carlo analysis. The structures were physically interpreted by introducing an appropriate intermolecular interaction. A 'bond' was then defined as an intermolecular connection that minimizes the energy of intermolecular interaction. However, their 'bond' energy is too weak for the 'bond' and the resulting network structure to be defined statically. The vertex-to-edge orientation between the nearest molecules is so ubiquitous that almost all of the molecules in the system can take part in the network, which is reflected in the appearance of a prepeak in the structure factor.

Structure of a molecular liquid GeI4.

A molecular liquid GeI4 is a candidate that undergoes a pressure-induced liquid-to-liquid phase transition. This study establishes the reference structure of the low-pressure liquid phase. Synchrotron x-ray diffraction measurements were carried out at several temperatures between the melting and the boiling points under ambient pressure. The molecule has regular tetrahedral symmetry, and the intramolecular Ge-I length of 2.51 Å is almost temperature-independent within the measured range. A reverse Monte Carlo (RMC) analysis is employed to find that the distribution of molecular centers remains self-similar against heating, and thus justifying the length-scaling method adopted in determining the density. The RMC analysis also reveals that the vertex-to-face orientation of the nearest molecules are not straightly aligned, but are inclined at about 20 degrees, thereby making the closest intermolecular I-I distance definitely shorter than the intramolecular one. The prepeak observed at ∼1 Å(-1) in the structural factor slightly shifts and increases in height with increasing temperature. The origin of the prepeak is clearly identified to be traces of the 111 diffraction peak in the crystalline state. The prepeak, assuming the residual spatial correlation between germanium sites in the densest direction, thus shifts toward lower wavenumbers with thermal expansion. The aspect that a relative reduction in molecular size associated with the volume expansion is responsible for the increase in the prepeak's height is confirmed by a simulation, in which the molecular size is changed.