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

• Published in: The Journal of chemical physics 2019-03, Vol.150 (11), p.114501-114501
• Main Authors: Fuchizaki, Kazuhiro, Sakagami, Takahiro, Iwayama, Hiroshi
• Format: Article
• Language: English
• Subjects: Ammonia; Broken symmetry; Crossovers; Deformation; Form factors; Monte Carlo simulation; Organic chemistry; Physics; Quantum chemistry; Symmetry; Transition pressure
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5061714

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.