Static electric quadrupole interaction of Ta- and Hf-ions in barium and lead titanate

The static electric quadrupole interaction of¹⁸¹Ta and¹⁷⁸Hf in polycrystalline barium and lead titanate at the site of titanium has been measured using time differential PAC and the Mössbauer effect. The electric field gradients (EFG) at room temperature at the¹⁸¹Ta nucleus are ¦V _zz¦=(3.6±0.2)·10¹⁷V/cm² in BaTiO₃ and ¦V _zz¦=(14.6±0.6)·10¹⁷ V/cm² in PbTiO₃. The temperature dependence of the quadrupole interaction has been studied giving the following EFG values: ¦V _zz¦=(2.4±0.2)·10¹⁷ V/cm² in the monoclinic and ¦V _zz¦=(1.1±0.3)·10¹⁷ V/cm² in the rhomboedral phase of BaTiO₃, and ¦V _zz¦=(15.7±0.6)·10¹⁷ V/cm² for¹⁸¹Ta/PbTiO ₃ at 77 °K. The EFG of¹⁷⁸Hf in PbTiO₃ has been derived from a Mössbauer effect experiment to beV _zz=+(10.7±0.5)·10¹⁷ V/cm². The results are compared with EFG's calculated in a point charge model and with experimental EFG's measured at⁴⁴Sc and⁵⁷Fe in the same titanates by other authors. Contributions of covalent bonds to the effective EFG's in perovskit crystals are discussed.