Second-order rutile-type to CaCl 2-type phase transition in β-MnO 2 at high pressure

Abstract

MnO 2 was studied in a diamond anvil cell by angle-dispersive X-ray diffraction up to 46 GPa using both an imaging plate and film. A phase transition from the tetragonal rutile-type phase to an orthorhombic phase was observed at below 1 GPa. The absence of discontinuity in the lattice constants and the zero volume change are indicative of a second order transition and the pressure dependence of the spontaneous strain indicates a transition pressure of 0.3 GPa. Rietveld refinements of the structure at high pressure confirmed that the orthorhombic phase has a CaCl 2-type structure, space group Pnnm, a = 4.437(3), b = 4.312(3), c = 2.862(2) A ̊ , x(O) = 0.339(1), y(O) = 0.278(2) with Z = 2 at 7.3 GPa . The angle of rotation of the MnO 6 octahedra about their two-fold axes parallel to c was found to increase from 3° at 1.0 GPa to 12° at 9.4 GPa. The p- V data for the orthorhombic phase were fitted using a Birch-Murnaghan equation of state yielding a bulk modulus of 328(18) GPa with a first pressure derivative of 4(2). The changes observed at this ferroelastic transition in MnO 2 present a model for the corresponding phase transition in stishovite-SiO 2 at high pressure.