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The charge density and bond character of the rutile-type structures of SiO 2 , GeO 2  and SnO 2  were studied by X-ray diffraction using monopole refinement. The refinement of the charge density was performed by least-squares refinement including the Κ-parameter and the electron population in the X-ray atomic scattering parameters. The oxygen′s Κ-parameters of three oxides are 0.91 (SiO 2 ), 1.06 (GeO 2 ), 1.14 (SnO 2 ). The oxygen valence electron of each sample is 1.06(8)e for SiO 2 , 1.10(16)e for GeO 2  and 1.13(15)e for SnO 2 . These values indicate that the electron distributions are more localized with an increase in the cation atomic number. The difference Fourier map of each sample shows the deformation density of the valence electrons of cations. The overlapping electron orbitals cause the deformation of MO 6  octahedra of rutile-type structures. The ratio between O-O shared and unshared edge and the ratio between the apical and equatorial M-O interatomic distances decrease with the cation ionicity and the repulsive force between the two cations in adjacent octahedra.

X-ray diffraction study of bond character of rutile-type SiO 2 , GeO 2 and SnO 2