Short-range interaction explanation of ferroelectric, antiferroelectric and proton glass behavior in pure RDP, ADP, and mixed RDP-ADP crystals respectively

Abstract

A unified model is presented for Rb1-x(NH4)xH2PO4 crystals over the whole range x=0 (RDP) to x=1 (ADP). Two short-range interactions are postulated. One is the Slater energy ε0 which is kept at the value for RDP for all x. The other is an interaction εa between two hydrogens in O-H...O bonds across an NH4+ ion from each other. It is responsible for the off-center positions observed for ammonium ions in the antiferroelectric phase of ADP. Its strength is assumed proportional to x. By minimizing the free energy, one finds a range of x for which no transition occurs, but instead proton glass behavior sets in. Fox x near 0 and 1 respectively, first-order ferroelectric and antiferroelectric transitions are predicted. Both phase boundaries are close to those observed experimentally.