Lattice-Dynamical Estimation of Atomic Displacement Parameters in Carbonates: Calcite and Aragonite CaCO3, Dolomite CaMg(CO3)2 and Magnesite MgCO3

Abstract

Using crystallographic information and empirical potentials derived from fitting the vibrational frequencies of all the substances under study, together with those of a group of silicates and oxides, a Born–von Karman rigid-ion lattice-dynamical model has been applied to the whole Brillouin zone in calcite, aragonite (α- and β-CaCO3, respectively), magnesite (MgCO3) and dolomite [CaMg(CO3)2]. The Raman and IR spectra are satisfactorily reproduced and interpreted by these calculations; there is also very good agreement with atomic anisotropic displacement parameters (a.d.p.'s) derived from accurate crystal structure refinement by various authors and with the experimental values of thermodynamic functions over a wide range of temperatures. On these vibrational grounds, the stability of calcite with respect to aragonite at high temperature can be accounted for.