Temperature dependence of the electric quadrupole interaction in PbHfO₃

The temperature dependence of the Electric Field Gradient (EFG) in PbHfO₃ was studied in the temperature range 25-225°C by the Differential Perturbed Angular Correlation method. In the two anti-ferroelectric phases below 215°C, not too close to either transition temperature, the EFG decreases as the temperature increases toward T_c. Just above T_c an abrupt rise of EFG was observed indicating a critically behaving contribution to EFG. The results are interpreted in terms of a model based on the local static as well as time-dependent changes of the electric environment, at a lattice site. In accord with the predictions of this model the results exhibit qualitatively the P²_s temperature dependence of EFG far from T_c, where P_s is the sub-lattice polarization, while in close proximity to T_c the dominant contribution to EFG is due to the susceptibility X_q connected with the soft-mode fluctuations. The derived critical exponents are in agreement with previous experimental results on related compounds and with theoretical predictions. A hitherto unobserved additional component of V_zz was established, behaving critically at the antiferro-paraelectric transition at 215°C. This new component is interpreted to originate in local fluctuations connected with the central mode.