Influence of N-H-O hydrogen bonds on the structure and properties of (K(1-x)(NH4)(x)H2PO4) proton glasses: a single crystal neutron diffraction study.

It has been known for quite some time now that proton dynamics plays a key role in the structural ferroelectric (FE)/antiferroelectric (AFE) phase transition in the crystals belonging to the potassium dihydrogen phosphate crystal family. Mixed crystals belonging to this family having the composition M(1-x)(NW(4))(x)W(2)AO(4), where M = K, Rb, Cs, W = H, D, and A = P, As, exhibit proton glass behavior due to frustration between FE and AFE ordering; these proton glasses do not undergo any structural phase change but retain their room temperature structure down to very low temperatures. Single crystal neutron diffraction investigations of four mixed crystals with composition (K(1-x)(NH(4))(x)H(2)PO(4)), where x = 0.0, 0.29, 0.67 1.0, were undertaken with the intention to investigate the effect of the local structural deviations on the overall average structure of the crystals and correlate these structural changes to the presence or absence of a structural phase transition in these crystals. Hydrogen bonding is shown to play a key role in the changing nature of the mixed crystals as the composition varies from the potassium rich ferroelectric region to the proton glass region to the ammonium rich antiferroelectric region.