Ammonium Fluoride as a Hydrogen-Disordering Agent for Ice

The removal of residual hydrogen disorder from various phases of ice with acid or base dopants at low temperatures has been a focus of intense research for many decades. As an antipode to these efforts, we now show using neutron diffraction that ammonium fluoride (NH4F) is a hydrogen-disordering agent for the hydrogen-ordered ice VIII. Cooling its hydrogen-disordered counterpart ice VII doped with 2.5 mol % ND4F under pressure leads to a hydrogen-disordered ice VIII with similar to 31% residual hydrogen disorder illustrating the long-range hydrogen-disordering effect of ND4F. The doped ice VII could be supercooled by similar to 20 K with respect to the hydrogen-ordering temperature of pure ice VU after which the hydrogen-ordering took place slowly over a similar to 60 K temperature window. These findings demonstrate that ND4F-doping slows down the hydrogen-ordering kinetics quite substantially. The partial hydrogen order of the doped sample is consistent with the antiferroelectric ordering of pure ice VIII. Yet, we argue that local ferroelectric domains must exist between ionic point defects of opposite charge. In addition to the long-range effect of NH4F-doping on hydrogen-ordered water structures, the design principle of using topological charges should be applicable to a wide range of other ice-rule systems including spin ices and related polar materials.