Structural, mechanical and vibrational study of uranyl silicate mineral soddyite by DFT calculations

Abstract

Uranyl silicate mineral soddyite, (UO)(SiO)·2(HO), is a fundamental component of the paragenetic sequence of secondary phases that arises from the weathering of uraninite ore deposits and corrosion of spent nuclear fuel. In this work, soddyite was studied by first principle calculations based on the density functional theory. As far as we know, this is the first time that soddyite structure is determined theoretically. The computed structure of soddyite reproduces the one determined experimentally by X-Ray diffraction (orthorhombic symmetry, spatial group Fddd O2; lattice parameters a = 8.334 Å, b = 11.212 Å; c = 18.668 Å). Lattice parameters, bond lengths, bond angles and X-Ray powder pattern were found to be in very good agreement with their experimental counterparts. Furthermore, the mechanical properties were obtained and the satisfaction of the Born conditions for mechanical stability of the structure was demonstrated by means of calculations of the elasticity tensor. The equation of state of soddyite was obtained by fitting lattice volumes and pressures to a fourth order Birch-Murnahan equation of state. The Raman spectrum was also computed by means of density functional perturbation theory and compared with the experimental spectrum obtained from a natural soddyite sample. The results were also found in agreement with the experimental data. A normal mode analysis of the theoretical spectra was carried out and used in order to assign the main bands of the Raman spectrum.