Electric field gradients and charge density in corundum, α-Al2O3

Abstract

The charge density in α-Al2O3 has been refined with respect to X-ray structure factors [complete spheres for both Mo Kα and Ag Kα radiations with (sin θ/λ)max = 1.19 and 1.495 Å-1 respectively] and electric-field gradient tensors at both atomic sites, using Hirshfeld- type deformation functions. Atomic charges from a κ refinement are + 1.32 (5) for Al and -0.88 (8) e for O. The charge distribution of O is polarized towards the four Al neighbours, and metal-metal bonds are clearly absent. Quadrupole coupling constants and asymmetry parameters of the field-gradient tensors cannot be determined from the structure factors. They define the quadrupolar deformations near the atomic centers, and the X-ray data define the charge density between the atoms. The orientational parameters of the tensors and the signs of their largest eigenvalues can be qualitatively retrieved from the X-ray data. The refinement of anisotropic secondary-extinction parameters may, however, destroy this information. Refinement with respect to the field gradients affects mainly the quadrupolar deformation terms, and has little influence on the X-ray scale factor (i.e. monopolar terms) and computed electrostatic fields (i.e. dipolar terms). Properties of the charge density with different angular symmetries are thus only weakly correlated.