Pressure-induced tricritical point in the ferroelectric phase transition of KH₂PO₄

Measurement of the net polarization charge of two KH₂PO₄ crystals as a function of temperature, applied electric field, and hydrostatic pressure indicates the existence of a tricritical point in the (2.3±0.3)-kbar pressure range. This result is based upon static measurements of the polarization response to applied dc field in a 0.5-K neighborhood of the ferroelectric transition at pressures of 0, 1, 2, 2.4, and 3 kbar. Unlike ³He- ⁴He mixtures and some metamagnets, for KH₂PO₄ the field which gives rise to the "wing" structure of the tricritical point is experimentally available. For each of the five pressures the paraelectric region is well described by the Landau equation of state, E=A₀(T-T₀)P+BP³+CP⁵, to within 0.05 K of the transition temperature. The exponent δ derived from our data at 3 kbar is in the crossover region between the critical value of 3 and the tricritical value of 5 predicted by Landau theory. At 2.4 kbar our derived value of δ is consistent with the tricritical value of 5. Analysis of the data along lines of constant polarization, which are here called "isopols," indicates that the transition is first order at 0 and 1 kbar with the critical field decreasing from 183±60 V/cm at 0 kbar to 43±13 V/cm at 1 kbar. At 3 kbar the B coefficient is positive which indicates a second-order transition. This observation of a change in the order of the transition is supported by a change in the behavior of the isothermal dielectric susceptibility which has a maximum for E>0 at 0.5 kbar and at E=0 at 3 kbar.