High‐pressure elasticity of stishovite and the P42/mnm ⇌ Pnnm phase transition

Abstract

A Landau free energy expansion has been developed to describe the elastic constant variations of stishovite (SiO2) associated with the P42/mnm (rutile‐type) ⇌ Pnnm (CaCl2‐type) phase transition as a function of pressure. The transition appears to display classical second‐order character, with an equilibrium transition pressure which is renormalized by coupling of the soft optic mode with spontaneous strain. Lattice parameter data from the literature show that the symmetry breaking strain is large, while the nonsymmetry breaking strains are small. These have been used to constrain the numerical values of the strain/order parameter coupling coefficients, which in turn have been used to constrain values for the Landau coefficients. When substituted into expressions for all the individual elastic constants, taking values for experimental and calculated values of the bare elastic constants from the literature, a clear view of the pattern of elastic constant variations is produced. Variations of P and S wave velocities derived from the calculated elastic constants for a second‐order transition show a dip as the transition point is approached from high pressure and from low pressure but do not show a discontinuity. The velocity anomaly provides a signature for the presence of free silica in the lower mantle.