V4+ doping into SiO2, ZrO2 and ZrSiO4 structures. An ab initio perturbed ion study



An ab initio perturbed ion study using X-ray diffraction data has been carried out for ZrSiO4 (zircon), ZrO2 (monoclinic zirconia, baddeleyite), and SiO2 (α-cristobalite) crystal lattice structures. The different substitutions of V4+ for Zr4+ and Si4+ occurring in these host lattices have been analyzed. Geometry optimizations have been performed with the aim of determining the relative stability, cell parameters, and force constants of radial displacement associated with the local relaxation for pure and doped structures. Numerical results are confronted against experimental data and compared with previous results. The geometrical cell parameters of different structures obtained by computer simulation and the results of the X-ray diffraction studies agree with previous experimental data. For the zircon lattice, the substitution of V4+ for Zr4+ at an eightfold-coordinated site is energetically favorable while the substitution of V4+ for Si4+ at a fourfold-coordinated site is unstable. For ZrO2, the substitution of V4+ for Zr4+ is energetically favorable while the substitution of V4+ for Si4+ in SiO2 is energetically unfavorable. There is less sensitive influence of the crystal lattice parameters for substitutions occurring at the eightfold-coordinated ion site in ZrSiO4 and SiO2 structures. The doping process produces a decrease of force constant (k) values associated with the breathing fundamental vibrational mode for all structures. The k associated with the radial displacement in dodecahedral substitution in the ZrSiO4 structure is especially high. The force constants for this movement in tetrahedral substitution in the ZrSiO4, ZrO2, and SiO2 structures have a lower value. The differences between ionic radii reported by Shannon and Prewitt of the species concerned in the doping process are not capable of explaining the relaxation of crystal lattice parameters in the ZrO2 and SiO2 structures. © 1993 John Wiley & Sons, Inc.