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The high-pressure solid phase of water known as ice VII has recently attracted a lot of attention when its presence was detected in large exoplanets, their icy satellites, and even in Earth's mantle. Moreover, a transition of ice VII to the superionic phase can be triggered by external electric fields. Here, we investigate the dielectric responses of ice VII to applied oscillating electric fields of various frequencies employing non-equilibrium ab initio molecular dynamics. We focus on the dynamical properties of a dipole-ordered ice VII structure, for which we explored external-field-induced electronic polarisation and the vibrational spectral density of states (VDOS). These analyses are important for the understanding of collective motions in the ice-VII lattice and the electronic properties of this exotic water phase.

Ice VII and ice X are the two most dominant phases, stable over a large pressure range between 2 and 150 GPa and made of fundamentally different chemical bonding. Yet, the two ice phases share a similar bcc-based crystal structure and lattice constants, resulting in a challenge to discern the crystal structure of ice VII and ice X. Here, we present well-resolved X-ray diffraction data of H2O in quasi-hydrostatic H2 and He pressure media, clearly resolving the two ice phases to 130 GPa and the dissociative nature of ice VII to X transition occurring at 20-50 GPa in H2O-H2 and 60-70 GPa in H2O-He. The present diffraction data permits, for the first time, the accurate determination of the bulk moduli B0 of 225 (or 228) GPa for ice X and 6.2 (or 4.5) GPa for ice VII, in H2O-H2 (or H2O-He), which can provide new constraints for Giant planetary models.

Ice amorphization, low- to high-density amorphous (LDA-HDA) transition, as well as (re)crystallization in ice, under compression have been studied extensively due to their fundamental importance in materials science and polyamorphism. However, the nature of the multiple-step "reverse" transformation from metastable high-pressure ice to the stable crystalline form under reduced pressure is not well understood. Here, we characterize the rate and temperature dependence of the structural evolution from ice VII to ice I recovered at low pressure (∼5 mTorr) using in situ time-resolved X-ray diffraction. Unlike previously reported ice VII (or ice VIII)→LDA→ice I transitions, we reveal three temperature-dependent successive transformations: conversion of ice VII into HDA, followed by HDA-to-LDA transition, and then crystallization of LDA into ice I. Significantly, the temperature-dependent characteristic times indicate distinctive thermal activation mechanisms above and below 110-115 K for both ice VIII-to-HDA and HDA-to-LDA transitions. Large-scale molecular-dynamics calculations show that the structural evolution from HDA to LDA is continuous and involves substantial movements of the water molecules at the nanoscale. The results provide a perspective on the interrelationship of polyamorphism and unravel its underpinning complexities in shaping ice-transition kinetic pathways.

Water has a rich phase diagram with several crystals, as confirmed by experiments. High-pressure and high-temperature water is of interest for Earth’s mantle and exoplanetary investigations. It is in this region of the phase diagram of water that new plastic crystal phases of water have been revealed via computer simulations by both classical forcefields and ab initio calculations. However, these plastic phases still remain elusive in experiments. Here, we present a complete characterization of the structure, dynamics, and thermodynamics of the computational plastic crystal phases of water using molecular dynamics and the two-phase thermodynamic method and uncover the interplay between them. The relaxation times of different reorientational correlation functions are obtained for the hypothetical body-centered-cubic and face-centered-cubic plastic crystal phases of water at T = 440 K and P = 8 GPa. Results are compared to a high pressure liquid and ice VII phases to improve the understanding of the plastic crystal phases. Entropy results indicate that the fcc crystal is more stable compared to the bcc structure under the studied conditions.

We have studied the ${\mathrm{H}}_{2}\mathrm{O}$ ice VII--ice X phase transition at room temperature by performing three quasicontinuous synchrotron time-resolved x-ray-diffraction experiments in a dynamic diamond anvil cell, reaching pressures of 180 GPa. The dense pressure coverage of our volume data allows us to directly derive the bulk modulus for ${\mathrm{H}}_{2}\mathrm{O}$ over the entire pressure range. Our data document three major changes in compression behavior in the ranges of 35--40, 50--55, and 90--110 GPa, likely corresponding to the formation of pretransition dynamically disordered ice VII and ice X, and static ice X, respectively. Our results confirm that ice X has a very high bulk modulus.

Using the Deep Potential methodology, we construct a model that reproduces accurately the potential energy surface of the SCAN approximation of density functional theory for water, from low temperature and pressure to about 2400 K and 50 GPa, excluding the vapor stability region. The computational efficiency of the model makes it possible to predict its phase diagram using molecular dynamics. Satisfactory overall agreement with experimental results is obtained. The fluid phases, molecular and ionic, and all the stable ice polymorphs, ordered and disordered, are predicted correctly, with the exception of ice III and XV that are stable in experiments, but metastable in the model. The evolution of the atomic dynamics upon heating, as ice VII transforms first into ice VII^{''} and then into an ionic fluid, reveals that molecular dissociation and breaking of the ice rules coexist with strong covalent fluctuations, explaining why only partial ionization was inferred in experiments.

Using a density-functional-theory-based approach, we explore the symmetrization and proton dynamics in ice-VII, for which recent high-pressure NMR experiments indicate significant proton dynamics in the pressure-range of $20-95$ GPa. We directly sample the potential seen by the proton and find a continuous transition from double- to single-well character over the pressure range of 2 to 130 GPa accompanied by proton dynamics in agreement with the NMR experiments., Comment: 7 pages, 6 figures

Starting from Shannon's definition of dynamic entropy, we proposed a simple theory to describe the transition between different rare event related dynamic states in condensed matters, and used it to investigate high pressure ice VII. Instead of the thermodynamic intensive quantities such as the temperature and pressure, a dynamic intensive quantity named dynamic field is taken as the controlling variable for the transition. Based on the dynamic entropy versus dynamic field curve, two dynamic states corresponding to ice VII and dynamic ice VII were discriminated rigorously in a pure dynamic view. Their microscopic differences were assigned to the dynamic patterns of proton transfer. This study puts a similar dynamical theory used in earlier studies of glass models on a simple and more fundamental basis, which could be applied to describe the dynamic states of realistic and more condensed matter systems., 5 pages, 4 figures

The phase diagram and melting curve of water ice is investigated up to 45 GPa and 1600 K by synchrotron x-ray diffraction in the resistively and laser heated diamond anvil cell. Our melting data evidence a triple point at 14.6 GPa, 850 K. The latter is shown to be related to a first-order solid transition from the dynamically disordered form of ice VII, denoted ice ${\mathrm{VII}}^{\ensuremath{'}}$, toward a high-temperature phase with the same bcc oxygen lattice but larger volume and higher entropy. Our experiments are compared to ab initio molecular dynamics simulations, enabling us to identify the high-temperature bcc phase with the predicted superionic ice ${\mathrm{VII}}^{\ensuremath{'}\ensuremath{'}}$ phase [J.-A. Hernandez and R. Caracas, Phys. Rev. Lett. 117, 135503 (2016).].

Fully anharmonic calculations of the dielectric response of insulators require costly $a\phantom{\rule{0}{0ex}}b$ $i\phantom{\rule{0}{0ex}}n\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}o$ molecular dynamics simulations. Here, the authors show that this electronic response property can be described efficiently by a deep neural network that retains the accuracy of $a\phantom{\rule{0}{0ex}}b$ $i\phantom{\rule{0}{0ex}}n\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}o$ molecular dynamics. The scheme is demonstrated with calculations of the infrared absorption spectrum of liquid water at standard conditions, and of the evolution of the spectrum of crystalline ice undergoing a pressure-induced structural transformation from molecular ice VII to ionic ice X.

The externally-heated diamond anvil cell (EHDAC) can be used to generate simultaneously high-pressure and high-temperature conditions found in Earth's and planetary interiors. Here we describe the design and fabrication of the EHDAC assemblies and accessories, including ring resistive heaters, thermal and electrical insulating layers, thermocouple placement, as well as the experimental protocol for preparing the EHDAC using these parts. The EHDAC can be routinely used to generate megabar pressures and up to 900 K temperatures in open air, and potentially higher temperatures up to ~1200 K with a protective atmosphere (i.e., Ar mixed with 1% H2). Compared with a laser-heating method for reaching temperatures typically >1100 K, external heating can be easily implemented and provide a more stable temperature at ≤900 K and less temperature gradients to the sample. We showcased the application of the EHDAC for synthesis of single crystal ice-VII and studied its single-crystal elastic properties using synchrotron-based X-ray diffraction and Brillouin scattering at simultaneously high-pressure high-temperature conditions.

To assess the performance of our implemented first principles isothermal-isobaric centroid molecular dynamics (CMD) we performed Born-Oppenheimer (BO) CMD simulations in the NPT ensemble for high pressure ices (HPIs) VIII, VII, and X at 270 K. By elevating pressure the crystal system is found to transform from tetragonal to cubic at ∼ 30 GPa, accompanying the proton order (ice VIII)-disorder (ice VII) transition observed to occur in our BO-CMD simulations. Moreover, our simulations are proved to be able to reproduce well both infrared and Raman spectra for HPIs in the frequency range above ∼ 500 cm−1.

Superionic behavior has been realized in ice VII by means of external electric fields., In a superionic (SI) ice phase, oxygen atoms remain crystallographically ordered while protons become fully diffusive as a result of intramolecular dissociation. Ice VII’s importance as a potential candidate for a SI ice phase has been conjectured from anomalous proton diffusivity data. Theoretical studies indicate possible SI prevalence in large-planet mantles (e.g., Uranus and Neptune) and exoplanets. Here, we realize sustainable SI behavior in ice VII by means of externally applied electric fields, using state-of-the-art nonequilibrium ab initio molecular dynamics to witness at first hand the protons’ fluid dance through a dipole-ordered ice VII lattice. We point out the possibility of SI ice VII on Venus, in its strong permanent electric field.

A wide variety of two-dimensional layered materials are synthesized by liquid-phase exfoliation. Here we examine exfoliation of MoS2 into nanosheets in a mixture of water and isopropanol (IPA) containing cavitation bubbles. Using force fields optimized with experimental data on interfacial energies between MoS2 and the solvent, multimillion-atom molecular dynamics simulations are performed in conjunction with experiments to examine shock-induced collapse of cavitation bubbles and the resulting exfoliation of MoS2. The collapse of cavitation bubbles generates high-speed nanojets and shock waves in the solvent. Large shear stresses due to the nanojet impact on MoS2 surfaces initiate exfoliation, and shock waves reflected from MoS2 surfaces enhance exfoliation. Structural correlations in the solvent indicate that shock induces an ice VII like motif in the first solvation shell of water.

Thermal transport in ice features an unusual response. In addition to its intrinsic scientific interest, an understanding of the mechanisms determining the thermal conductivity of ice might be relevant in climate modelling and planetary science. Accurate microscopic models can provide important molecular insight into these mechanisms. In this work, we quantify using molecular simulations and state of the art forcefields, the thermal conductivity of ice Ih, VI, VII and a plastic phase that has been proposed very recently at pressures in the GPa range. The TIP4P models used in this study underestimate significantly the thermal conductivity of ice Ih and ice VII, while they show good agreement with experimental measurements of ice VI. The discrepancies observed are examined by investigating the temperature dependence of the thermal conductivity. The simulations indicate that the models are too anharmonic and they potentially feature a higher structural disorder than the experimental systems. We suggest that at high pressures the simulated thermal conductivities can be rationalized in terms of the performance of the models in predicting the equation of state of ice. The thermal conductivity of the plastic phase is very similar to that of the coexisting ice VII. Since the water molecules in the plastic phase feature orientational disorder, these results indicate that the hydrogen bond network does not play a significant role in defining the thermal transport mechanisms of ice at high pressures.

We report a new ice phase that forms spontaneously at the interface between ice VII and liquid water in molecular dynamics simulations of TIP4P/2005 water. The new phase is structurally quite similar to an ice phase originally found to be a precursor in the course of the homogeneous nucleation of ice VII in liquid water. A part of the water molecules in these ice phases can rotate easily because the number of hydrogen bonds in them is less than four, and thus they can be regarded as partial plastic phases. A rough estimate suggests that these phases are thermodynamically more stable than either ice VI or ice VII for 3 GPa < P < 18 GPa at T = 300 K. Although the partial plastic phases would be metastable states at any point in the phase diagram of real water, they might be realized experimentally with the aid of dopants and/or solid surfaces.

The mechanism of how ice crystal form has been extensively studied by many researchers but remains an open question. Molecular dynamics (MD) simulations are a useful tool for investigating the molecular-scale mechanism of crystal formation. However, the timescale of phenomena that can be analyzed by MD simulations is typically restricted to microseconds or less, which is far too short to explore ice crystal formation that occurs in real systems. In this study, a metadynamics (MTD) method was adopted to overcome this timescale limitation of MD simulations. An MD simulation combined with the MTD method, in which two discrete oxygen–oxygen radial distribution functions represented by Gaussian window functions were used as collective variables, successfully reproduced the formation of several different ice crystals when the Gaussian window functions were set at appropriate oxygen–oxygen distances: cubic ice, stacking disordered ice consisting of cubic ice and hexagonal ice, high-pressure ice VII, layered ice with an ice VII structure, and layered ice with an unknown structure. The free-energy landscape generated by the MTD method suggests that the formation of each ice crystal occurred via high-density water with a similar structure to the formed ice crystal. The present method can be used not only to study the mechanism of crystal formation but also to search for new crystals in real systems.

High pressure Nuclear Magnetic Resonance (NMR) is known to uncover behavior of matter at extreme conditions. However, significant maintenance demands, space requirements and high costs of superconducting magnets render its application unfeasible for regular modern high pressure laboratories. Here, we present a table-top NMR system based on permanent Halbach magnet arrays with dimensions of 25 cm diameter and 4 cm height. At the highest field of 1013 mT, 1H-NMR spectra of Ice VII have been recorded at 25 GPa and ambient temperature. The table-top NMR system can be used together with double sided laser heating set-ups. Feasibility of high-pressure high-temperature NMR was demonstrated by collecting 1H-NMR spectra of H2O at 25 GPa and 1063(50) K. We found that the change in signal intensity in laser-heated NMR diamond anvil cell yields a convenient way for temperature measurements.

Helmholtz energy of ice VII&ndash, X is determined in a pressure regime extending to 450 GPa at 300 K using local-basis-functions in the form of b-splines. The new representation for the equation of state is embedded in a physics-based inverse theory framework of parameter estimation. Selected pressures as a function of volume from 14 prior experimental studies and two theoretical studies constrain the behavior of Helmholtz energy. Separately measured bulk moduli, not used to construct the representation, are accurately replicated below about 20 GPa and above 60 GPa. In the intermediate range of pressure, the experimentally determined moduli are larger and have greater scatter than values predicted using the Helmholtz representation. Although systematic error in the determination of elastic moduli is possible and likely, the alternative hypothesis is a slow relaxation time associated with changes in proton mobility or the ice VII to X transition. A correlation is observed between anomalies in the pressure derivative of the predicted bulk modulus and previously suggested higher-order phase transitions. Improved determinations of elastic properties at high pressure would allow refinement of the current equation of state. More generally, the current method of data assimilation is broadly applicable to other materials in high-pressure studies and for investigations of planetary interiors.

Helmholtz energy of ice VII–X is determined in a pressure regime extending to 450 GPa at 300 K using local-basis-functions in the form of b-splines. The new representation for the equation of state is embedded in a physics-based inverse theory framework of parameter estimation. Selected pressures as a function of volume from 14 prior experimental studies and two theoretical studies constrain the behavior of Helmholtz energy. Separately measured bulk moduli, not used to construct the representation, are accurately replicated below about 20 GPa and above 60 GPa. In the intermediate range of pressure, the experimentally determined moduli are larger and have greater scatter than values predicted using the Helmholtz representation. Although systematic error in the determination of elastic moduli is possible and likely, the alternative hypothesis is a slow relaxation time associated with changes in proton mobility or the ice VII to X transition. A correlation is observed between anomalies in the pressure derivative of the predicted bulk modulus and previously suggested higher-order phase transitions. Improved determinations of elastic properties at high pressure would allow refinement of the current equation of state. More generally, the current method of data assimilation is broadly applicable to other materials in high-pressure studies and for investigations of planetary interiors.

We have collected neutron-diffraction data of sufficient quality for structural refinement from deuterated ice VII to over 60 GPa. At these pressures, we are approaching the onset of molecular dissociation where the water molecule should be significantly distorted. We fitted our data with both the conventional structural model for ice VII and a recently proposed “interstitial” model. We found these to be statistically indistinguishable and, therefore, adopted the conventional model in this work. Our refinements yield the first direct experimental determination of the molecular structure in this pressure regime. They show a clear elongation of the covalent bond, the rate of which rapidly increases with pressure, indicating we have entered a distinct regime on theapproach to ice X. In addition, we have directly measured the pressure dependence of the separation of the two equivalent deuteron sites along the hydrogen bonds, which provides an upper bound on the hydrogen-bondcentering pressure.

Neutron diffraction experiments of ice VII at pressures up to 6.2 GPa and 10.2 kV/mm were conducted to investigate the potential ferroelectrically ordered structure of ice VII induced by a high electric field. To accomplish this, we developed a high-pressure cell assembly to allow for powder neutron diffraction to be conducted under both high-pressure and high-electric field conditions. However, the subsequent observed diffraction patterns taken in situ at these conditions do not show sufficient evidence of the proposed ferroelectrically ordered structure of ice VII. We estimate the degree of the hydrogen ordering in ice VII under the applied conditions from high-pressure $P\ensuremath{-}E$ loop measurements, and discuss the future possibilities of detecting the ferroelectrically ordered structure.

In situ Raman spectroscopy revealed that transiting the concentrated NaI/H2O solutions to an ice VI phase and then into an ice VII phase at 298 K proceeds in a way different from that activated by the solute type. Unlike the solute type that raises both the critical pressures PC1 and PC2, for the liquid-VI, the VI-VII transition simultaneously occurs in the Hofmeister series order: I > Br > Cl > F ∼ 0; concentration increase raises the PC1 faster than the PC2 that remains almost constant at higher NaI/H2O molecular number ratios. Concentration increase moves the PC1 along the liquid-VI phase boundary and it finally merges with PC2 at the triple-phase junction featured at 350 K and 3.05 GPa. The highly-deformed H-O bond is less sensitive to the concentration because of the involvement of anion-anion repulsion that weakens the electric field in the hydration shells. Observations confirm that the salt solvation lengthens the O:H nonbond and softens its phonon but relaxes the H-O bond contrastingly. Compression, however, has the opposite effect from that of salt solvation. Therefore, compression recovers the polarization-deformed O:H-O bond first and then proceeds to the phase transitions. The anion-anion interaction discriminates the effect of NaI/H2O concentration from that of the solute type at an identical concentration on the phase transitions.

Context. Planetary mass and radius data are showing a wide variety in densities of low-mass exoplanets. This includes sub-Neptunes, whose low densities can be explained with the presence of a volatile-rich layer. Water is one of the most abundant volatiles, which can be in the form of different phases depending on the planetary surface conditions. To constrain their composition and interior structure, it is required to develop models that calculate accurately the properties of water at its different phases. Aims. We present an interior structure model that includes a multiphase water layer with steam, supercritical and condensed phases. We derive the constraints for planetary compositional parameters and their uncertainties, focusing on the multiplanetary system TRAPPIST-1, which presents both warm and temperate planets. Methods. We use a 1D steam atmosphere in radiative-convective equilibrium with an interior whose water layer is in supercritical phase self-consistently. For temperate surface conditions, we implement liquid and ice Ih to ice VII phases in the hydrosphere. We adopt a MCMC inversion scheme to derive the probability distributions of core and water compositional parameters Results. We refine the composition of all planets and derive atmospheric parameters for planets b and c. The latter would be in a post-runaway greenhouse state and could be extended enough to be probed by space mission such as JWST. Planets d to h present condensed ice phases, with maximum water mass fractions below 20%. Conclusions. The derived amounts of water for TRAPPIST-1 planets show a general increase with semi-major axis, with the exception of planet d. This deviation from the trend could be due to formation mechanisms, such as migration and an enrichment of water in the region where planet d formed, or an extended CO$_{2}$-rich atmosphere., 11 pages, 7 figures. Accepted by Astronomy & Astrophysics (in press)

We report a molecular dynamics simulation study of dense ice modeled by the reactive force field (ReaxFF) potential, focusing on the possibility of phase changes between crystalline and plastic phases as observed in earlier simulation studies with rigid water models. It is demonstrated that the present model system exhibits phase transitions, or crossovers, among ice VII and two plastic ices with face-centered cubic (fcc) and body-centered cubic (bcc) lattice structures. The phase diagram derived from the ReaxFF potential is different from those of the rigid water models in that the bcc plastic phase lies on the high-pressure side of ice VII and does the fcc plastic phase on the low-pressure side of ice VII. The phase boundary between the fcc and bcc plastic phases on the pressure, temperature plane extends to the high-temperature region from the triple point of ice VII, fcc plastic, and bcc plastic phases. Proton hopping, i.e., delocalization of a proton, along between two neighboring oxygen atoms in dense ice is observed for the ReaxFF potential but only at pressures and temperatures both much higher than those at which ice VII-plastic ice transitions are observed.

High-pressure and high-temperature experiments were performed to investigate the stability of methane hydrate under 6–40 GPa and 298–573 K using synchrotron X-ray powder diffraction in combination with a diamond anvil cell. The results thus obtained revealed that methane hydrate decomposes into solid methane and ice VII at temperatures considerably lower than the melting curves of solid methane and ice VII in the pressure range of 6–40 GPa.

The sensing capabilities of gold nanorods under high-pressure conditions were investigated in methanol-ethanol mixtures (up to 13 GPa) and in water (up to 9 GPa) through their optical extinction. The longitudinal SPR band of AuNR exhibits a redshift with pressure which is the result of two main competing effects: compression of the conduction electrons which increases the bulk plasma frequency (blueshift) and increase in the solvent density (redshift). The variation in de SPR peak wavelength allows us to estimate the bulk modulus of the gold nanoparticles with a precision of 10 % and to obtain analytical functions providing the pressure dependence of the refractive index of water in three phases: liquid, ice VI and ice VII. Furthermore, the SPR band shows abrupt jumps at the liquid to ice phase VI and ice phase VII transitions, which are in accordance with the first-order character of these transitions. Financial support from Project PGC2018-101464-B-I00 (FEDER) and MALTA-Consolider Team (RED2018-102612-T) of the Ministerio de Ciencia, Innovación y Universidades is acknowledged.

Gold nanorods (Au NRs), nanospheres and other nanoparticles display numerous superior physicochemical properties, such as resistance to oxidation and aggressive agents, strong enhancement of local electric field and a high absorption coefficient in the visible and near-infrared (NIR) range. The absorption peaks of surface plasmon resonance (SPR) in Au NRs are highly sensitive to their surrounding medium and to its refractive index (RI) changes. However, no applications of NRs for detecting phase transitions have been reported. Here, we show that Au NRs effectively detect phase transitions of compressed compounds, liquid and solid, by measuring their RI. Owing to the direct interaction of the NRs with their surrounding medium, its subtle RI changes can be observed by the use of high-pressure absorption vis-NIR spectroscopy. We have applied a Au NR-based sensor in a diamond anvil cell (DAC) for monitoring the phase transitions of compressed water, its freezing to ice VI and at the subsequent solid-solid phase transition to ice VII, and the monotonic compression and solid-solid phase transitions in urea and thiourea.

Structural transformations originating from diverse rearrangements of the hydrogen bonding in water create various phases. Although most phases have been well investigated down to the molecular level, the molecular structure of the nanomeniscus, a ubiquitous form of nanoscale water in nature, still remains unexplored. Here, we demonstrate that the water nanomeniscus exhibits the stable, ice-VII-like molecular structure in ambient condition. Surface-enhanced Raman spectroscopy on trace amounts of water, confined in inter-nanoparticle gaps, shows a narrowed tetrahedral peak at 3340 cm-1 in the OH-stretching band as well as a lattice-vibrational mode at 230 cm-1. In particular, the ice-VII-like characteristics are evidenced by the spectral independence with respect to temperature variations and differing surface types including the material, size and shape of nanoparticles. Our results provide un unambiguous identification of the molecular structure of nanoconfined water, which is useful for understanding the molecular aspects of water in various nanoscale, including biological, environments., Ice-VII, the densest phase of ice, has been expected to exist only under extreme conditions, such as in Earth’s deep mantle. Shin et al. show spectroscopic evidence that ice-VII-like structures can also be found in water confined in the nanomeniscus between packed nanoparticles at ambient conditions.

A typical vibrational spectrum in the ice phase has four separate bands: Translation, libration, bending, and stretching. Ice X, the final ice phase under high pressure, shows an exotic vibrational spectrum. Based on harmonic approximation, an ideal crystal of ice X has one peak, at 998 cm&minus, 1, for Raman scattering and two peaks, at 450 cm&minus, 1 and 1507 cm&minus, 1, for infrared absorption in this work. These three characteristic peaks are indicators of the phase transition between ice VII and VIII and ice X. Despite many experimental and theoretical works on ice X, only this study has clearly indicated these characteristic peaks in the region of the IR band. The phonon density of states shows quite different features than ice VIII, which could be verified by inelastic neutron scattering in the future. The dynamic processes of 15 vibrational normal modes are discussed and the typical hydrogen bonds are missing.

Understanding the behavior of materials at extreme pressures is a central issue in fields like aerodynamics, astronomy, and geology, as well as for advancing technological grand challenges such as inertial confinement fusion. Dynamic compression experiments to probe high-pressure states often encounter rapid phase transitions that may cause the materials to behave in unexpected ways, and understanding the kinetics of these phase transitions remains an area of great interest. In this review, we examine experimental and theoretical/computational efforts to study the freezing kinetics of water to a high-pressure solid phase known as ice VII. We first present a detailed analysis of dynamic compression experiments in which water has been observed to freeze on sub-microsecond time scales to ice VII. This is followed by a discussion of the limitations of currently available molecular and continuum simulation methods in modeling these experiments. We then describe how our phase transition kinetics models, which are based on classical nucleation theory, provide a more physics-based framework that overcomes some of these limitations. Finally, we give suggestions on future experimental and modeling work on the liquid-ice VII transition, including an outline of the development of a predictive multiscale model in which molecular and continuum simulations are intimately coupled.

Accurate modeling of planetary interiors requires that the pressure–volume–temperature ( PVT ) properties of phases present within the body be well understood. The high-pressure polymorphs of H 2 O have been studied extensively due to the abundance of ice phases in icy moons and, likely, vast number of extra-solar planetary bodies, with only select studies evaluating impurity-laden ices. In this study, ice formed from a 1.6 mol percent KCl-bearing aqueous solution was studied up to 32.89 ± 0.19 GPa and 625 K, and the incorporation of K + and Cl − ionic impurities into the ice VII structure was documented. The compression data at 295 K were fit with a third order Birch–Murnaghan equation of state and yielded a bulk modulus ( K T 0 ), its pressure derivative ( K T 0 ′ ), and zero pressure volume ( V 0 ) of 24.7 ± 0.9 GPa, 4.44 ± 0.09, and 39.2 ± 0.2 A 3 , respectively. The impurity-laden ice was found to be 6–8% denser than ice VII formed from pure H 2 O. Thermal expansion coefficients were also determined for several isothermal compression curves at elevated temperatures, and a PVT equation of state was obtained. The melting curve of ice VII with incorporated K + and Cl − was estimated by fitting experimental data up to 10.2 ± 0.4 GPa, where melting occurred at 625 K, to the Simon–Glatzel equation. The melting curve of this impurity-laden ice is systematically depressed relative to that of pure H 2 O by approximately 45 K and 80 K at 4 and 11 GPa, respectively. A portion of the K + and Cl − contained within the ice VII structure was observed to exsolve with increasing temperature. This suggests that an internal differentiating process could concentrate a K-rich phase deep within H 2 O-rich planets, and we speculate that this could supply an additional source of heat through the radioactive decay of 40 K. Our data illustrate ice VII can incorporate significant concentrations of K + and Cl − and increasing the possibility of deep-sourced and solute-rich plumes in moderate to large sized H 2 O-rich planetary bodies.

In situ Raman spectroscopy revealed that transiting H2O/NaX (∼64) solutions into an ice VI phase and then into an ice VII phase at a temperature of 298 K requires excessive pressures with respect to pure water. The increase of the critical pressures varies with the solute type in the Hofmeister series order: X = I > Br > Cl > F ∼ 0. The results suggest that the solute hydration creates electric fields that lengthen and soften the O:H nonbond and meanwhile shorten and stiffen the H–O bond through O–O Coulomb repulsion. Compression, however, does the opposite to solute electrification upon the O:H–O bond relaxation. Therefore, compression of the aqueous solutions recovers the electrification-deformed O:H–O bond first and then proceeds to the phase transitions, which requires excessive energy for the same sequence of phase transitions. Ice exclusion of solute disperses the frequencies of characteristic phonons and the critical pressures with unlikely new bond formation.

Hydrogen bond symmetrisations in H-bonded systems triggered by pressure-induced nuclear quantum effects (NQEs) is a long-known concept but experimental evidence in high-pressure ices has remained elusive with conventional methods. Theoretical works predicted quantum-mechanical tunneling of protons within water ices to occur at pressures above 30 GPa, and the H-bond symmetrisation transition to occur above 60 GPa. Here we used 1H-NMR on high-pressure ice up to 97 GPa, and demonstrate that NQEs govern the behavior of the hydrogen bonded protons in ice VII already at significantly lower pressures than previously expected. A pronounced tunneling mode was found to be present up to the highest pressures of 97 GPa, well into the stability field of ice X, where NQEs are not anticipated in a fully symmetrised H-bond network. We found two distinct transitions in the NMR shift data at about 20 GPa and 75 GPa attributed to the step-wise symmetrisation of the H-bond., Hydrogen atoms in water ices, under pressures at which they might exist in ocean exoplanets and icy moons, exhibit dynamics that are still poorly understood. Here, 1H-NMR experiments approaching the Mbar range shed light on the symmetrisation of hydrogen bonds preceding and accompanying the transformation of ice VII into ice X.

The nuclear quantum effects (NQEs) on the structural, elastic, electronic, and vibrational properties of high pressure ices (HPIs) VIII, VII, and X at 270 K were investigated via first principles centroid molecular dynamics (CMD). Our simulations clearly show that even at relatively high temperature of 270 K, the NQEs play a definite role in the pressure-induced proton order (ice VIII)-disorder (ice VII) transition occurring at ∼30 GPa in our H2O ice and the subsequent transition to the symmetric phase ice X suggested to occur at ∼80 GPa. The internal pressure computed at constant NVT conditions shows that the NQEs manifest themselves in the equation of state of HPIs. Our employed approach based on first principles CMD for computing vibrational spectra is proved to be able to reproduce well the overall features of the measured infrared and Raman spectra.

Encapsulating Earth's deep water filter Small inclusions in diamonds brought up from the mantle provide valuable clues to the mineralogy and chemistry of parts of Earth that we cannot otherwise sample. Tschauner et al. found inclusions of the high-pressure form of water called ice-VII in diamonds sourced from between 410 and 660 km depth, the part of the mantle known as the transition zone. The transition zone is a region where the stable minerals have high water storage capacity. The inclusions suggest that local aqueous pockets form at the transition zone boundary owing to the release of chemically bound water as rock cycles in and out of this region. Science , this issue p. 1136

An intense picosecond laser pulse focused into a liquid medium generates a shock wave in the focal region. This shock wave while propagating into the medium varies the pressure and temperature of the liquid locally leading to the appearance of novel phases which are manifested by the appearance of Raman peaks. We present the phase changes of ammonium nitrate (AN) dissolved in water by studying the forward and backward stimulated Raman Scattering (FSRS and BSRS) signals due to propagation of 30 ps laser pulse induced shockwaves. The dominant peak corresponding to the NO3− symmetric stretching mode is observed with a Raman shift of 1045 cm−1 which represents phase IV of AN with an orthogonal crystalline structure. Apart from this peak, the dominant mode of liquid phase of water with a Raman shift of 3400 cm−1 and an ice VII peak at a Raman shift of 3050 cm−1 confirming the pressure of 10 GPa is observed. The effect of the concentration and input energy on the appearance of the phases will be presented.

Water ice is a molecular solid whose behavior under compression reveals the interplay of covalent bonding in molecules and forces acting between them. This interplay determines high-pressure phase transitions, the elastic and plastic behavior of H 2 O ice, which are the properties needed for modeling the convection and internal structure of the giant planets and moons of the solar system as well as H 2 O-rich exoplanets. We investigated experimentally and theoretically elastic properties and phase transitions of cubic H 2 O ice at room temperature and high pressures between 10 and 82 GPa. The time-domain Brillouin scattering (TDBS) technique was used to measure longitudinal sound velocities (V L) in polycrystalline ice samples compressed in a diamond anvil cell. The high spatial resolution of the TDBS technique revealed variations of V L caused by elastic anisotropy, allowing us to reliably determine the fastest and the slowest sound velocity in a single crystal of cubic H 2 O ice and thus to evaluate existing equations of state. Pressure dependencies of the single-crystal elastic moduli C ij (P) of cubic H 2 O ice to 82 GPa have been obtained which indicate its hardness and brittleness. These results were compared with ab initio calculations. It is suggested that the transition from molecular ice VII to ionic ice X occurs at much higher pressures than proposed earlier, probably above 80 GPa.

We present equations of state relevant to conditions encountered in ramp and multiple-shock compression experiments of water. These experiments compress water from ambient conditions to pressures as high as about 14 GPa and temperatures of up to several hundreds of Kelvin. Water may freeze into ice VII during this process. Although there are several studies on the thermodynamic properties of ice VII, an accurate and analytic free energy model from which all other properties may be derived in a thermodynamically consistent manner has not been previously determined. We have developed such a free energy model for ice VII that is calibrated with pressure-volume-temperature measurements and melt curve data. Furthermore, we show that liquid water in the pressure and temperature range of interest is well-represented by a simple Mie-Gruneisen equation of state. Our liquid water and ice VII equations of state are validated by comparing to sound speed and Hugoniot data. Although they are targeted towards ramp and multiple-shock compression experiments, we demonstrate that our equations of state also behave reasonably well at pressures and temperatures that lie somewhat beyond those found in the experiments.

Time-resolved x-ray diffraction (XRD) of compressed liquid water shows transformation to ice VII in 6 nsec, revealing crystallization rather than amorphous solidification during compression freezing. Application of classical nucleation theory indicates heterogeneous nucleation and one-dimensional (e.g., needlelike) growth. These first XRD data demonstrate rapid growth kinetics of ice VII with implications for fundamental physics of diffusion-mediated crystallization and thermodynamic modeling of collision or impact events on ice-rich planetary bodies.

In the context of friction we use atomistic molecular-dynamics simulations to investigate water confined between graphene sheets over a wide range of pressures. We find that thermal equilibration of the confined water is hindered at high pressures. We demonstrate that, under the right conditions, square ice can form in an asperity, and that it is similar to cubic ice VII and ice X. We simulate sliding of atomically flat graphite on the square ice and find extremely low friction due to structural superlubricity. The conditions needed for square ice to form correspond to low sliding speeds, and we suggest that the ice observed in experiments of friction on wet graphite is of this type., Comment: 7 pages, 5 figures

We propose a spin model compatible with ice VII-plastic ice phase transitions and critical phenomena discovered recently by computer simulations. The Blume-Capel spin-1 Ising model is extended in order to describe the entropic stabilization effect in the plastic ice phase. The model shares the same set of tricritical exponents with simulation, indicating that they are of the same universality class.

Species dissolved in H 2 fluid were investigated in a SiO 2 –H 2 system. Raman and infrared (IR) spectra were measured at high pressure and room temperature after heating experiments were conducted at two pressure and temperature conditions: 2.0 GPa, 1700 K and 3.0 GPa, 1500 K. With the dissolution of quartz, a SiH vibration mode assignable to SiH 4 was detected from Raman spectra of the fluid phase. Furthermore, an OH vibration mode was observed at 3260 cm −1 from the IR spectra at 3.0 GPa. With decreasing pressure, the OH vibration frequencies observed between 3.0 and 2.1 GPa correspond to that of ice VII, and those observed at 1.4 and 1.1 GPa correspond to that of ice VI. These results indicate that the chemical reaction between dissolved SiO 2 components and H 2 fluid caused the formation of H 2 O and SiH 4 , which was contrastive to that observed in SiO 2 –H 2 O fluid. Results imply that a part of H 2 is oxidized to form H 2 O when SiO 2 components of mantle minerals dissolve in H 2 fluid, even in an iron-free system.

High pressure experiments were performed on D2O ice VII using a diamond anvil cell in a pressure range of 2.0–60 GPa at room temperature. In situ X-ray diffractometry revealed that the structure changed from cubic to a low symmetry phase at approximately 11 GPa, based on the observed splitting of the cubic structure's diffraction lines. Heating treatments were added for the samples to reduce the effect of non-hydrostatic stress. After heating, splitting diffraction lines became sharp and the splitting was clearly retained. Although symmetry and structure of the transformed phase have not been determined, change in volumes vs. pressure was calculated, assuming that the low-symmetry phase had a tetragonal structure. The bulk modulus calculated for the low-symmetry phase was slightly larger than that for the cubic structure. In Raman spectroscopy, the squared vibrational frequencies of ν1 (A1g), as a function of pressure, showed a clear change in the slope at 11–13 GPa. The full width at half maxima of the O...