Hexagonal diamond has been predicted computationally to display extraordinary physical properties including a hardness that exceeds cubic diamond. However, a recent electron microscopy study has shown that so-called hexagonal diamond samples are in fact not discrete materials but faulted and twinned cubic diamond. We now provide a quantitative analysis of cubic and hexagonal stacking in diamond samples by analysing X-ray diffraction data with the DIFFaX software package. The highest fractions of hexagonal stacking we find in materials which were previously referred to as hexagonal diamond are below 60%. The remainder of the stacking sequences are cubic. We show that the cubic and hexagonal sequences are interlaced in a complex way and that naturally occurring Lonsdaleite is not a simple phase mixture of cubic and hexagonal diamond. Instead, it is structurally best described as stacking disordered diamond. The future experimental challenge will be to prepare diamond samples beyond 60% hexagonality and towards the so far elusive 'perfect' hexagonal diamond.2

The glass transitions of low-density amorphous ice (LDA) and high-density amorphous ice (HDA) are the topic of controversial discussions. Understanding their exact nature may be the key to explaining the anomalies of liquid water but has also got implications in the general context of polyamorphism, the occurrence of multiple amorphous forms of the same material. We first show that the glass transition of hydrogen-disordered ice VI is associated with the kinetic unfreezing of molecular reorientation dynamics by measuring the calorimetric responses of the corresponding H2O, H2(18)O, and D2O materials in combination with X-ray diffraction. Well-relaxed LDA and HDA show identical isotopic-response patterns in calorimetry as ice VI, and we conclude that the glass transitions of the amorphous ices are also governed by molecular reorientation processes. This "reorientation scenario" seems to resolve the previously conflicting viewpoints and is consistent with the fragile-to-strong transition from water to the amorphous ices.

The reversible phase transition from hydrochloric-acid-doped ice VI to its hydrogen-ordered counterpart ice XV is followed using differential scanning calorimetry. Upon cooling at ambient pressure fast hydrogen ordering is observed at first followed by a slower process which manifests as a tail to the initial sharp exotherm. The residual hydrogen disorder in H2O and D2O ice XV is determined as a function of the cooling rate. We conclude that it will be difficult to obtain fully hydrogen-ordered ice XV by cooling at ambient pressure. Our new experimental findings are discussed in the context of recent computational work on ice XV.

The DO ice VI to ice XV hydrogen ordering phase transition at ambient pressure is investigated in detail with neutron diffraction. The lattice constants are found to be sensitive indicators for hydrogen ordering. The a and b lattice constants contract whereas a pronounced expansion in c is found upon hydrogen ordering. Overall, the hydrogen ordering transition goes along with a small increase in volume, which explains why the phase transition is more difficult to observe upon cooling under pressure. Slow-cooling ice VI at 1.4 GPa gives essentially fully hydrogen-disordered ice VI. Consistent with earlier studies, the ice XV obtained after slow-cooling at ambient pressure is best described with P-1 space group symmetry. Using a new modelling approach, we achieve the atomistic reconstruction of a supercell structure that is consistent with the average partially ordered structure derived from Rietveld refinements. This shows that C-type networks are most prevalent in ice XV, but other structural motifs outside of the classifications of the fully hydrogen-ordered networks are identified as well. The recently proposed Pmmn structural model for ice XV is found to be incompatible with our diffraction data, and we argue that only structural models that are capable of describing full hydrogen order should be used.

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