Doping-enhanced dipolar dynamics in ice V as a precursor of hydrogen ordering in ice XIII

Köster, K. W.; Raidt, A.; Fuentes-Landete, Violeta; Gainaru, C.; Loerting, Thomas; Böhmer, Roland

doi:10.1103/physrevb.94.184306

Cited by 20 publications

(35 citation statements)

References 73 publications

(131 reference statements)

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“…Dielectric loss spectra of the crystalline ice phases (a) I h (present work), (b) IV (present work), (c) V, 51 (d) VI (present work), and (e) XII 50. The dashed lines refer to power laws ε ′′ ∝ ν -α as indicated.…”

mentioning

confidence: 83%

“…3, we compile ambient-pressure dielectric loss spectra for the crystalline ice phases I h (hexagonal ice), 67 IV, and VI (all measured in the course of this work) as well as for ice V 51 and ice XII. 50 These (and other nominally pure) crystalline ices are well known to display orientational glass transitions. 46,[68][69][70] During such a transition, the hydrogen degrees of freedom freeze upon cooling, giving rise to a calorimetrically detectable signature, while the crystalline center-of-mass lattice remains unaffected.…”

Section: Crystalline Icesmentioning

confidence: 99%

“…While numerous results are available for ices studied under high pressure, 40 here we focus on ambientpressure data for hexagonal ice [54][55][56][57][58][59][60] and phases that were prepared under high-pressure conditions. The present compilation includes previously published results for ice V 51 and ice XII, 50 as well as data on the ices IV, VI, and the CO 2 -filled Sχ clathrate hydrate. In the present context, it is important to realize that OCO is a linear and symmetric moiety so that it lacks a molecular dipole moment.…”

Section: Introductionmentioning

confidence: 99%

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Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology

Münzner

Hoffmann

Böhmer

et al. 2019

The Journal of Chemical Physics

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To characterize the structural relaxation of an aqueous solution of LiCl, frequency-dependent shear rheological experiments are carried out near its glass transition. Analyzed within the fluidity representation, the generic spectral shape that was previously found for a range of different kinds of glass formers is confirmed for the currently studied hydrogen-bonded fluid as well. Furthermore, the validity of the rheological equivalent of the Barton-Nakajima-Namikawa relation is demonstrated for the aqueous LiCl solution. Its mechanical response is compared with that obtained using dielectric spectroscopy, a technique which is sensitive to both the reorientational dynamics of the water molecules and the translational dynamics of the ionic species. The extent to which these electrical polarization processes are coupled to those governing the viscoelastic response is discussed, also in comparison with the behavior of other ion conducting liquids.

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mentioning

confidence: 83%

Section: Crystalline Icesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology

Münzner

Hoffmann

Böhmer

et al. 2019

The Journal of Chemical Physics

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“…Subsequently, the samples are quench recovered to ambient pressure and then transferred under liquid nitrogen to the calorimeter or to a Dewar that is shipped to Dortmund where the dielectric measurements are carried out. A description of the procedures relevant for the dielectric experiments can be found elsewhere [14,24].…”

Section: Methodsmentioning

confidence: 99%

“…Dopants have allowed one to unlock kinetically hindered but thermodynamically favored transitions to hydrogen-ordered ices [16]. The role of these dopants is to enhance microscopic dynamics [18,24,25]. This enhancement is key to inducing hydrogen-ordering transitions at T < 150 K, where otherwise molecular motion is too slow for ordering processes to take place on typical laboratory timescales.…”

Section: B Glass and Hydrogen-ordering Transitions In Crystalline Icesmentioning

confidence: 99%

Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments

et al. 2019

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Based on calorimetry and dielectric spectroscopy, the influence of dopants as well as H/D-isotope substitution on the dynamics and thermodynamics of expanded high-density amorphous ice (eHDA) is studied. We find that dopants do not significantly alter the phase behavior, the dielectric relaxation times, and the calorimetric glass transition of eHDA. These observations starkly contrast those made for crystalline ices such as ice I h , ice V, ice VI, and ice XII, where suitable dopants enhance the dielectric dynamics by several orders of magnitude and can trigger hydrogen order-disorder transitions, then taking place below the orientational glass transition temperature of undoped samples. This conspicuous contrast to the behavior of crystalline ices strongly argues against point-defect dynamics in amorphous ices and against a previously suggested "crystallinelike" nature of the amorphous ices. Furthermore, H/D substitution also does not affect the calorimetric glass transition in eHDA much, whereas for crystalline ices, the heat capacity increase at the glass transition is roughly halved. In addition, the H/D-isotope shift of the glass transition onset is much larger for crystalline ices than it is for amorphous ices. This observation favors the notion of eHDA's glass transition as a glass-to-liquid transition and is evidence against a mere molecular-reorientation unfreezing at water's second glass transition. Comparing the isotope effect on activation energies for dielectric relaxation with ice V suggests that in amorphous ice water molecules move translationally above T g. Thus, the present work strongly supports that above this glass transition, water does indeed exist in its contested high-density liquid state.

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Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing

Štůsek,

Veselý,

Melicharová

et al. 2024

J. Phys. Chem. C

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Freezing and its application is growing in popularity, yet the understanding of the nonequilibrium transformations and acidity changes that occur in frozen solutions upon thawing have remained relatively unexplored. By contrast to other acids such as nitric acid and sulfuric acid, not even the phase diagram is known fully for hydrochloric acid. Even more importantly, the nonequilibrium transformations upon heating glassy freeze-concentrated solution (FCS) are also not well understood and freeze concentration lacks quantification. This work rectifies the knowledge gap by providing the freeze-concentration factors on the example of hydrochloric acid. For this purpose, we have used differential scanning calorimetry to reveal phase changes upon heating. UV−vis spectroscopy of acid−base indicators is employed to elucidate acidity changes. All the samples reach negative values of the Hammett acidity function from −2.5 to −0.25 after freezing, showing that aqueous HCl can freeze concentrate 7−250,000 times depending on its initial concentration. We observe the glass-to-liquid transition of the freeze-concentrated glassy solution above −140 °C and cold crystallization of the ultraviscous FCS to HCl hydrates above −110 °C. Cold crystallization leads to basification, whereas acidification accompanies the subsequent melting of the eutectic ice/HCl-hexahydrate. Finally, melting of the ice immersed in solution shows basification caused by the dilution with meltwater. High (1 M) and low (<10 mM) concentrations freeze homogeneously, whereas intermediate concentrations reveal the presence of freeze-concentrated regions of higher and lower concentrations having distinct glass transition and melting temperatures.

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Doping-enhanced dipolar dynamics in ice V as a precursor of hydrogen ordering in ice XIII

Cited by 20 publications

References 73 publications

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology

Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments

Acidity and Phase Behavior of Frozen Hydrochloric Acid during Thawing

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