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Bulk moduli and high-pressure crystal structures of minium, Pb₃O₄, determined by X-ray powder diffraction

¹ Max-Planck-Institute for Solid State Research, Heisenbergstrasse 1, D-70569 Stuttgart, Germany
² MAX-lab, Lund University, P.O. Box 118, SE-22100 Lund, Sweden
³ Experiments Division High Pressure Group, European Synchrotron Radiation Facility, B.P. 220, F-38043 Grenoble CEDEX, France

Correspondence: ^* E-mail: m.jansen{at}fkf.mpg.de

We report the pressure dependence of the crystal structure of lead tetroxide (p 41.05 GPa, T = 298 K) using high-resolution angle-dispersive X-ray powder diffraction. Pb₃O₄ shows two reversible phase transitions in the measured pressure range. The crystal structures of the modifications identified have in common frameworks of Pb⁺⁴O₆ octahedra and irregular Pb⁺²O₄₊₁ respectively Pb²⁺O₆₊₁ polyhedra. At ambient conditions, Pb₃O₄ crystallizes in space group P4₂/mbc (phase I). Between 0.11 and 0.3 GPa it exhibits a displacive second order phase transition to a structure with space group Pbam (phase II). A second displacive phase transition occurs between 5.54 and 6.6 GPa to another structure with space group Pbam (phase III) but halved c dimension. A non-linear compression behavior over the entire pressure range is observed, which can be described by two Vinet relations in the ranges from 0.28 to 5.54 GPa and from 6.6 to 41.05 GPa. The extrapolated bulk moduli of the high-pressure phases were determined to be K₀ = 21(2) GPa for phase II and K₀ = 91(3) GPa for phase III. The crystal structures of all phases were refined from X-ray diffraction powder data collected at several pressures between 0.06 and 41.05 GPa. Except for their cell dimensions, phases I and II were found to be isostructural to the corresponding phases at low temperatures, whereas phase III can be derived from the Sr₂PbO₄ aristotype. With increasing pressure, the lone pair which is localized at Pb²⁺ adopts increasingly pure s-character, which is reflected by the similar coordination polyhedra of Pb²⁺ in Pb₃O₄ (phase III) and of Sr²⁺ in Sr₂PbO₄.

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