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

S AhlmannLars HoffmannM KepplerPhilipp MünznerChristina M TonauerThomas LoertingCatalin GainaruRoland Böhmer
Published in: Physical chemistry chemical physics : PCCP (2022)
The glass transitions of amorphous ices as well as of aqueous phosphoric acid solutions were reported to display very large 1 H/ 2 H 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 16 O/ 18 O isotope effects are missing, the latter scenario was previously favored for the amorphous ices. Considering the dielectric results on 18 O 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 1 H/ 2 H isotopically mixed and 18 O 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.
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