Pressure-induced toroidal order in molecular Sn2P2S6 ferroelectrics
Abstract
For the Sn2P2S6 crystalline compound with a rich temperature--pressure phase diagram that contains the ferroelectric phase, semiconductor-to-metal transition, and superconductive state, ab initio molecular dynamics calculations were performed on a single unit cell and on a superstructure using an evolutionary algorithm in combination with density functional theory calculations to study structural transformations resulting from rearrangements in chemical bonds under pressure. The structure models of the pressure-induced lowest energy phases in the molecular Sn2P2S6 crystal demonstrate the possibility of space-arranged chains or rings of P2S6 molecules. Pressure can break P-P bonds of P2S6 molecules, causing one of the phosphorous atoms to displace into the sulfur-formed octahedron and providing another phosphorous atom into an octahedral coordination with two tin atoms and four sulfur atoms. The results of the modeling correlate with the gradual rise of deviation of the pressure dependence of the unit cell volume of the Sn2P2S6 structure, as determined by X-ray diffraction experiments, from the dependence calculated with the Birch-Murnaghan equation of state. It also reveals toroidally ordered local dipoles in the centrosymmetric phase, which may be related to the previously observed superconductivity in the high-pressure metallic phase of Sn2P2S6.
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