Pressure-induced Pb-Pb bonding and phase transition in Pb2SnO4

Acta Crystallogr B Struct Sci Cryst Eng Mater. 2020 Dec 1;76(Pt 6):979-991. doi: 10.1107/S205252062001238X. Epub 2020 Nov 3.

Abstract

High-pressure single-crystal to 20 GPa and powder diffraction measurements to 50 GPa, show that the structure of Pb2SnO4 strongly distorts on compression with an elongation of one axis. A structural phase transition occurs between 10 GPa and 12 GPa, with a change of space group from Pbam to Pnam. The resistivity decreases by more than six orders of magnitude when pressure is increased from ambient conditions to 50 GPa. This insulator-to-semiconductor transition is accompanied by a reversible appearance change from transparent to opaque. Density functional theory-based calculations show that at ambient conditions the channels in the structure host the stereochemically-active Pb 6s2 lone electron pairs. On compression the lone electron pairs form bonds between Pb2+ ions. Also provided is an assignment of irreducible representations to the experimentally observed Raman bands.

Keywords: density functional theory; high-pressure X-ray diffraction; insulator–semiconductor transition; lead stannate (Pb2SnO4); pressure-induced phase transition.