Isotope effects on the dynamics of amorphous ices and aqueous phosphoric acid solutions

The glass transitions of amorphous ices as well as of aqueous phosphoric acid solutions were reported to display very large ¹H/²H isotope effects. Using dielectric spectroscopy, in both types of glassformers for equimolar protonated/deuterated mixtures an almost ideal isotope-mixing behavior rather than a bimodal relaxation is found. For the amorphous ices this finding is interpreted in terms of a glass-to-liquid rather than an orientational glass transition scenario. Based on calorimetric results revealing that major ¹⁶O/¹⁸O isotope effects are missing, the latter scenario was previously favored for the amorphous ices. Considering the dielectric results on ¹⁸O substituted amorphous ices and by comparison with corresponding results for the aqueous phosphoric acid solutions, it is argued that the present findings are compatible with the glass-to-liquid scenario. To provide additional information regarding the deeply supercooled state of ¹H/²H isotopically mixed and ¹⁸O substituted glassformers, the aqueous phosphoric acid solutions are studied using shear mechanical spectroscopy as well, a technique which so far could not successfully be applied to characterize the glass transitions of the amorphous ices.