Accurate and precise lattice parameters of HO and DO ice Ih between 1.6 and 270 K from high-resolution time-of-flight neutron powder diffraction data.

Accurate and precise lattice parameters for DO and HO varieties of hexagonal ice (ice Ih, space group P6/mmc) have been obtained in the range 1.6 to 270 K. Precision of the lattice parameters (∼0.0002% in a and 0.0004% in c for DO, 0.0008% in a and 0.0015% in c for HO) is ensured by use of the time-of-flight method on one of the longest primary neutron flight-path instruments in the world, the High-Resolution Powder Diffractometer at the ISIS neutron source. These data provide a more precise description of the negative thermal expansion of the material at low temperatures than the previous synchrotron gold standard' [Röttger et al. (1994). Acta Cryst. B50, 644-648], including the region below 10 K where the lattice parameters saturate. The volume expansivity of both isotopologues turns negative below 59-60 K, in excellent agreement with a recent dilatometry study. The axial expansivities are highly isotropic (differing by < 1% in DO ice Ih). Furthermore, the c/a ratio of different DO ice samples exhibit a statistically significant dispersion of ∼0.015% below 150 K that appears to depend on the thermal history of the sample, which disappears on warming above 150 K. Similarly, HO ice exhibits a kink' in the c/a ratio at ∼115 K. The most plausible explanation is a freezing-in of the molecular reorientation process on cooling and subsequent relaxation on warming.