Ionic network analysis of tectosilicates: the example of coesite at variable pressure

Abstract

The method of ionic network analysis [Thomas (2017).Acta Cryst.B73, 74–86] is extended to tectosilicates through the example of coesite, the high-pressure polymorph of SiO2. The structural refinements of Černoket al.[Z. Kristallogr.(2014),229, 761–773] are taken as the starting point for applying the method. Its purpose is to predict the unit-cell parameters and atomic coordinates at (p–T–X) values in-between those of diffraction experiments. The essential development step for tectosilicates is to define a pseudocubic parameterization of the O4cages of the SiO4tetrahedra. The six parametersaPC,bPC,cPC, αPC, βPCand γPCallow a full quantification of the tetrahedral structure,i.e.distortion and enclosed volume. Structural predictions for coesite require that two separate quasi-planar networks are defined, one for the silicon ions and the other for the O4cage midpoints. A set of parametric curves is used to describe the evolution with pressure of these networks and the pseudocubic parameters. These are derived by fitting to the crystallographic data. Application of the method to monoclinic feldspars and to quartz and cristobalite is discussed. Further, a novel two-parameter quantification of the degree of tetrahedral distortion is described. At pressures in excess ofca20.45 GPa it is not possible to find a self-consistent solution to the parametric curves for coesite, pointing to the likelihood of a phase transition.