Origin of the low-temperature endotherm of acid-doped ice VI: new hydrogen-ordered phase of ice or deep glassy states?

On the basis of a low-temperature endotherm, it has recently been argued that cooling acid-doped ice VI at high pressures leads to a new hydrogen-ordered phase. We show that the endotherms are in fact caused by the glass transitions of deep glassy states related to ice VI. As expected for such endothermic overshoot effects, they display a characteristic dependence on pressure and cooling rate, they can be produced by sub-T(g) annealing at ambient pressure, and they can be made to appear or disappear depending on the heating rate and the initial extent of relaxation. It is stressed that the existence of a new crystalline phase, as it has been suggested, cannot depend on the heating rate at which it is heated. X-ray diffraction shows that samples for which the low-temperature endotherm is present, weak or absent, as observed at a heating rate of 5 K min(–1), are structurally very similar. Furthermore, we show that the reported shifts of the (102) Bragg peak upon heating are fully consistent with our scenario and also with our earlier neutron diffraction study. Deuterated acid-doped ice VI cooled at high pressure also displays a low-temperature endotherm and its neutron diffraction pattern is consistent with deep glassy ice VI. Accessing deep glassy states of ice with the help of acid doping opens up a fascinating new chapter in ice research. Compared to pure ice VI, the glass transition temperature is lowered by more than 30 K by the acid dopant. Future work should focus on the deep glassy states related to all the other hydrogen-disordered ices including the ‘ordinary’ ice Ih.