Kinetic isotope effects on hydrogen/deuterium disordering and ordering in ice crystals: A Raman and dielectric study of ice VI, XV, and XIX.

Ice XIX and ice XV are both partly hydrogen-ordered counterparts to disordered ice VI. The ice XIX → XV transition represents the only order-to-order transition in ice physics. Using Raman and dielectric spectroscopies, we investigate the ambient-pressure kinetics of the two individual steps in this transition in real time (of hours), that is, ice XIX → transient ice VI (the latter called VI‡) and ice VI‡ → ice XV. Hydrogen-disordered ice VI‡ appears intermittent between 101 and 120 K, as inferred from the appearance and subsequent disappearance of the ice VI Raman marker bands. A comparison of the rate constants for the H2O ices reported here with those from D2O samples [Thoeny et al., J. Chem. Phys. 156, 154507 (2022)] reveals a large kinetic isotope effect for the ice XIX decay, but a much smaller one for the ice XV buildup. An enhancement of the classical overbarrier rate through quantum tunneling for the former can provide a possible explanation for this finding. The activation barriers for both transitions are in the 18-24 kJ/mol range, which corresponds to the energy required to break a single hydrogen bond. These barriers do not show an H/D isotope effect and are the same, no matter whether they are derived from Raman scattering or from dielectric spectroscopy. These findings favor the notion that a dipolar reorientation, involving the breakage of a hydrogen bond, is the rate determining step at the order-to-order transition.

Raman spectroscopy study of the slow order-order transformation of deuterium atoms: Ice XIX decay and ice XV formation.

The nature of the hydrogen substructure of a deuterated and deuterium chloride (DCI)-doped ice VI sample after cooling at 1.8 GPa has been a topic of recent interest-especially because the novel ice polymorph ice XIX was discovered in the course of such studies. We here investigate deuterated samples containing 5% H2O using Raman spectroscopy to probe for transitions associated with rearrangement of D-atoms in ice XIX. The protocol involving heating at subambient pressure (10 mbar) in this study follows closely the one used in our earlier neutron diffraction study. Heating of ice XIX induces a complex cascade of processes involving both ordering and disordering of D atoms. Our Raman spectra demonstrate that the transition sequence is ice XIX → ice VI‡ → ice XV, in accordance with our earlier neutron diffraction result. First signs for ice XIX decay are evident at 100 K, while ice XV build-up is seen only at 108 K and above. Between 100 and 108 K, a transiently disordered D-substructure appears, where at 108 K, ice VI‡ forms from ice XIX and simultaneously decays to produce ice XV-thereby establishing a dynamic equilibrium. Using isothermal, time-resolved Raman spectroscopy in real time, we here determine rate constants, Avrami exponents, and activation energies for both slow processes, ice XIX decay and ice XV build-up. The first transition in this sequence, ice XIX decay, is faster than the second transition, ice XV build-up, so that ice VI‡ accumulates. On the basis of the Johnson-Mehl-Avrami-Kolmogorov data obtained from the isothermal Raman experiment, we additionally report kinetic models for the development of fractions of ices XIX, XV, and VI‡ in non-isothermal heating experiments at different heating rates. These models consider the two coupled first-order transitions as separated processes, where the phase fractions are calculated for incrementally small temperature (or time) steps. These models compare favorably with our previous observations for slowly or rapidly heated ice XIX samples, such as in calorimetry or neutron diffraction experiments.

Near-Infrared Spectra of High-Density Crystalline H2O Ices II, IV, V, VI, IX, and XII.

High-pressure ice polymorphs are important for our understanding of hydrogen bonding and exist in the interior of the earth and icy moons. Nonetheless, spectroscopic information about them is scarce, where no information about their optical properties in the near-infrared (NIR) region is available at all. We here report NIR spectra of six ice polymorphs differing in terms of their density and O-atom topology, namely, ices II, IV, V, VI, IX, and XII, in comparison with the known spectra of ice Ih. By contrast to earlier work, we do not use mulling agents or transmission of thin films but use diffuse reflectance on powdered samples in liquid nitrogen. The first overtone of the OH-stretching mode is identified as the marker band most suitable to distinguish between these ices. There is a clear blue shift of this band that increases with increasing topological density in addition to a significant narrowing of the band.

Co-deposition of gas hydrates by pressurized thermal evaporation.

Gas hydrates are usually synthesized by bringing together a pressurized gas and liquid or solid water. In both cases, the transport of gas or water to the hydrate growth site is hindered once an initial film of hydrate has grown at the water-gas interface. A seemingly forgotten gas-phase technique overcomes this problem by slowly depositing water vapor on a cold surface in the presence of the pressurized guest gas. Despite being used for the synthesis of low-formation-pressure hydrates, it has not yet been tested for hydrates of CO2 and CH4. Moreover, the potential of the technique for the study of hydrate decomposition has not been recognized yet. We employ two advanced implementations of the condensation technique to form hydrates of CO2 and CH4 and demonstrate the applicability of the process for the study of hydrate decomposition and the phenomenon of self-preservation. Our results show that CO2 and CH4 hydrate samples deposited on graphite at 261-265 K are almost pure hydrates with an ice fraction of less than 8%. Rapid depressurization experiments with thin deposits (approx. 330 µm thickness) of CO2 hydrate on an aluminum surface at 265 K yield identical dissociation curves when the deposition is done at identical pressure. However, hydrates deposited at 1 MPa almost completely withstand decomposition after rapid depressurization to 0.1 MPa, while samples deposited at 2 MPa decompose 7 times faster. Therefore, this synthesis technique is not only applicable for the study of hydrate decomposition but can also be used for the controlled deposition of a super-preserved hydrate.

Distinguishing ice ß-XV from deep glassy ice VI: Raman spectroscopy.

The nature of the hydrogen sublattice of an HCl-doped ice VI sample after cooling at 1.8 GPa has been a topic of recent interest. The samples are interpreted either as the new H-ordered ice phase ice ß-XV with a thermodynamic stability region in the phase diagram [T. M. Gasser et al., Chem. Sci., 2018, 9, 4224], or alternatively as H-disordered, deep glassy ice VI [A. Rosu-Finsen and C. G. Salzmann, Chem. Sci., 2019, 10, 515]. Here we provide a comprehensive Raman spectroscopic study on ice ß-XV, ice XV and ice VI, with the following key findings: (i) the Raman spectra of ice ß-XV differ fundamentally from those of ice VI and ice XV, where the degree of H-order is even higher than in ice XV. (ii) Upon cooling ice VI there is competition between formation of ice XV and ice ß-XV domains, where ice XV forms at 0.0 GPa, but ice ß-XV at 1.8 GPa. Domains of ice ß-XV are present in literature "ice XV" at 1.0 GPa. This result clarifies the puzzling earlier observation that the degree of H-order in ice XV apparently improves upon heating and recooling at ambient pressure. In reality, this procedure leaves the H-order in ice XV unaffected, but removes ice ß-XV domains by transforming them to ice XV. (iii) Upon heating, the samples experience the transition sequence ice ß-XV → ice XV → ice VI, i.e., an order-order transition at 103 K followed by an order-disorder transition at 129 K. The former progresses via a disordered transient state. (iv) D2O ice ß-XV forms upon cooling DCl-doped D2O-ice VI, albeit at a much lower pace than in the hydrogenated case so that untransformed D2O ice VI domains are present even after slow cooling. The librational band at 380 cm-1 is identified to be the characteristic spectroscopic feature of deuterated ice ß-XV. Taken together these findings clarify open questions in previous work on H-ordering in the ice VI lattice, rule out a glassy nature of ice ß-XV and pave the way for a future neutron diffraction study to refine the crystal structure of D2O ice ß-XV.

Vitrification and increase of basicity in between ice Ih crystals in rapidly frozen dilute NaCl aqueous solutions.

The freezing of ionic aqueous solutions is common in both nature and human-conducted cryopreservation. The cooling rate and the dimensions constraining the solution are known to fundamentally influence the physicochemical characteristics of the sample, including the extent of vitrification, morphology, and distribution of ions. The presence of some salts in an aqueous solution often suppresses the ice crystallization, allowing bulk vitrification during relatively slow cooling. Such a process, however, does not occur in NaCl solutions, previously observed to vitrify only under hyperquenching and/or in sub-micrometric confinements. This work demonstrates that, at freezing rates of ≥100 K min-1, crystallized ice Ih expels the freeze-concentrated solution onto the surfaces of the crystals, forming lamellae and veins to produce glass, besides eutectic crystallization. The vitrification covers (6.8% ± 0.6%) and (17.9% ± 1.5%) of the total eutectic content in 0.06M and 3.4 mM solutions, respectively. The vitrified solution shows a glass-to-liquid transition succeeded by cold crystallization of NaCl · 2H2O during heating via differential scanning calorimetry. We establish that ice crystallization is accompanied by increased basicity in freeze-concentrated solutions, reflecting preferential incorporation of chloride anions over sodium cations into the ice. After the sample is heated above the glass transition temperature, the acidity gradually returns towards the original value. The morphology of the samples is visualized with an environmental scanning electron microscope. Generally, the method of vitrifying the freeze-concentrated solution in between the ice Ih crystals via fast cooling can be considered a facile route towards information on vitrified solutions.

Configurational entropy of ice XIX and its isotope effect.

Ice XIX is a partly hydrogen-ordered polymorph related to disordered ice VI, similar to ice XV. We here investigate the order-order-disorder sequence ice XIX→ice XV→ice VI based on calorimetry at ambient pressure both for D2O and H2O-ice XIX. From these data we extract configurational entropy differences between ice XIX, ice XV and ice VI. This task is complex because, unlike for all other ices, the order-disorder transition from ice XIX to ice VI takes place in two steps via ice XV. Even more challenging, these two steps take place in an overlapping manner, so that careful separation of slow kinetics is necessary. This is evidenced best by changing the heating rate in calorimetry experiments: For fast heating experiments the second step, disordering of ice XV, is suppressed because the first step, formation of ice XV from ice XIX, is too slow. The transient state ice VI‡ that is initially produced upon ice XIX decay then does not have enough time to convert to ice XV, but remains disordered all along. In order to tackle the challenge to determine the entropy difference between ice XIX and VI as well as the entropy difference between ice XV and VI we employ two different approaches that allow assessing the impact of kinetics on the entropy change. "Single peak integration" defines a kinetically limited result, but "combined peak integration" allows estimation of the true thermodynamic values. Our best estimate for the true value shows ice XIX to be much more ordered than ice XV (25 ± 3% vs 9 ± 4% of the Pauling entropy). For D2Oice XIX samples we obtain 28% of order, but only when a small number of fast H-isotope defects are used. In the second part we use these results to estimate the location of the ice XIX phase boundary both for protiated and deuterated ice XIX. The initial Clapeyron slope at ambient pressure is determined from the combination of neutron powder diffraction volume differences and calorimetry entropy differences data to be 21 K GPa-1 with an order-disorder transition temperature To-d(0.0 GPa) = 103 ± 1 K. An in situ bracketing experiment at 1.8 GPa yields To-d(1.8 GPa) = 116 ± 3 K, i.e., the phase boundary slope flattens at higher pressures. These data allow us to determine the region of thermodynamic stability of ice XIX in the phase diagram and to explain the surprising isotope shift reversal at 1.6 GPa compared to 0.0 GPa, i.e., why D2O-ice XIX disorders at lower temperatures than H2O-ice XIX at 1.6 GPa, but at higher temperatures at ambient pressures.

Calorimetric Investigation of Hydrogen-Atom Sublattice Transitions in the Ice VI/XV/XIX Trio.

Ice XIX represents the latest discovery of ice polymorphs and exists in the medium pressure range near 1-2 GPa. Ice XIX is a partially hydrogen-ordered phase, by contrast to its disordered mother phase ice VI, which shares the same oxygen-atom network with ice XIX. Ice XIX differs in terms of the ordering of the hydrogen-atom sublattice, and hence the space group, from its hydrogen-ordered sibling ice XV, which also features the same type of oxygen network. Together, ice VI, XV, and XIX form the only known trio of ice polymorphs, where polymorphic transformations from order to order, order to disorder, and disorder to order are possible, which also compete with each other depending on the thermodynamic path taken and the cooling/heating rates employed. These transitions in the H-sublattice have barely been investigated, so we study here the unique triangular relation in the ice VI/XV/XIX trio based on calorimetry experiments. We reveal the following key features for H-sublattice transitions: (i) upon cooling ice VI, domains of ice XV and XIX develop simultaneously, where pure ice XV forms at ≤0.85 GPa and pure ice XIX forms at ≥1.60 GPa, (ii) ice XIX transforms into ice XV via a transient disordered state, (iii) ice XV recooled at ambient pressure features a complex domain structure, possibly containing an unknown H-ordered polymorph, (iv) recooled ice XV partly transforms back into ice XIX at 1.80 GPa, and (v) partial deuteration slows down domain reordering strongly. These findings not only are of interest in understanding possible hydrogen-ordering and -disordering processes in the interior of icy moons and planets but, more importantly, also provide a challenging benchmark for our understanding and parameterizing many-body interactions in H-bonded networks.

Structural characterization of ice XIX as the second polymorph related to ice VI.

Ice polymorphs usually appear as hydrogen disorder-order pairs. Ice VI has a wide range of thermodynamic stability and exists in the interior of Earth and icy moons. Our previous work suggested ice ß-XV as a second polymorph deriving from disordered ice VI, in addition to ice XV. Here we report thermal and structural characterization of the previously inaccessible deuterated polymorph using ex situ calorimetry and high-resolution neutron powder diffraction. Ice ß-XV, now called ice XIX, is shown to be partially antiferroelectrically ordered and crystallising in a √2×√2×1 supercell. Our powder data recorded at subambient pressure fit best to the structural model in space group [Formula: see text]. Key to the synthesis of deuterated ice XIX is the use of a DCl-doped D2O/H2O mixture, where the small H2O fraction enhances ice XIX nucleation kinetics. In addition, we observe the transition from ice XIX to its sibling ice XV upon heating, which proceeds via a transition state (ice VI‡) containing a disordered H-sublattice. To the best of our knowledge this represents the first order-order transition known in ice physics.

Experiments indicating a second hydrogen ordered phase of ice VI.

In the last twelve years five new ice phases were experimentally prepared. Two of them are empty clathrate hydrates and three of them represent hydrogen ordered counterparts of previously known disordered ice phases. Here, we report on hydrogen ordering in ice VI samples produced by cooling at pressures up to 2.00 GPa. Based on results from calorimetry, dielectric relaxation spectroscopy, Raman spectroscopy, and powder X-ray diffraction the existence of a second hydrogen ordered polymorph related to ice VI is suggested. Powder X-ray data show the oxygen network to be the one of ice VI. For the 1.80 GPa sample the activation energy from dielectric spectroscopy is 45 kJ mol-1, which is much larger than for the known hydrogen ordered proxy of ice VI, ice XV. Raman spectroscopy indicates the 1.80 GPa sample to be more ordered than ice XV. It is further distinct from ice XV in that it experiences hydrogen disordering above ≈103 K which is 26 K below the ice XV to ice VI disordering transition. Consequently, below 103 K it is thermodynamically more stable than ice XV, adding a stability region to the phase diagram of water. For the time being we suggest to call this new phase ice ß-XV and to relabel it ice XVIII once its crystal structure is known.