Ice XII Research Articles

Thermodynamically Stable Intermediate in the Course of Hydrogen Ordering from Ice V to Ice XIII.

Even though many partially ordered ices are known, it remains elusive to understand and categorize them. In this study, we study the ordering from ice V to XIII using calorimetry at ambient pressure and discover that the transition takes place via an intermediate that is thermodynamically stable at 113-120 K. Our isothermal ordering approach allows us to highlight the distinction of this intermediate from ice V and XIII, where there are clear differences both in terms of enthalpy and ordering kinetics. We suggest that the approach developed in the present work can also reveal the nature of partially ordered forms in the hydrogen order-disorder series of other ice phases.

Detailed crystallographic analysis of the ice V to ice XIII hydrogen-ordering phase transition

Ice V is a structurally highly complex material with 28 water molecules in its monoclinic unit cell. It is classified as a hydrogen-disordered phase of ice. Yet, some of its hydrogen-bonded water molecules display significant orientational order. Upon cooling pure ice V, additional orientational ordering cannot be achieved on the experimental time scale. Doping with hydrochloric acid has been shown to be most effective in enabling the phase transition of ice V to its hydrogen-ordered counterpart ice XIII. Here, we present a detailed crystallographic study of this phase transition investigating the effects of hydrochloric and hydrofluoric acid as well as lithium and potassium hydroxide doping. The magnitudes of the stepwise changes in the lattice constants during the phase transition are found to be more sensitive indicators for the extent of hydrogen order in ice XIII than the appearance of new Bragg peaks. Hydrofluoric acid and lithium hydroxide doping enable similar ordering processes as hydrochloric acid but with slower kinetics. The various possible space groups and ordered configurations of ice XIII are examined systematically, and the previously determined P21/a structure is confirmed. Interestingly, the partial hydrogen order already present in ice V is found to perpetuate into ice XIII, and these ordering processes are found to be independent of pressure. Overall, the hydrogen ordering goes along with a small increase in volume, which appears to be the origin of the slower hydrogen-ordering kinetics under pressure. Heating pressure-quenched samples at ambient pressure revealed low-temperature "transient ordering" features in both diffraction and calorimetry.

Two basic vibrational modes of hydrogen bonds in ice XIII

Using a first-principles density functional theory method, we calculated the vibrational spectrum of ice XIII. In combination with spectroscopic experiments, we demonstrated that the two characteristic hydrogen bond (H-bond) peaks in the translational region of ice V (the hydrogen-disordered counterpart of ice XIII) recorded by inelastic neutron scattering originate from two basic H-bond vibrational modes. We first observed this phenomenon when studying ice Ic and then confirmed it when studying ice XIV, XVI, and XVII. This study of high-pressure ice XIII supports our theory that two basic H-bond modes exist as a general rule among the ice family. The “isolated O–H vibration modes” found by Whale et al. when studying ice XV are also discussed in this work.

2D IR spectroscopy of high-pressure phases of ice.

We present experimental and simulated 2D IR spectra of some high-pressure forms of isotope-pure D2O ice and compare the results to those of ice Ih published previously [F. Perakis and P. Hamm, Phys. Chem. Chem. Phys. 14, 6250 (2012); L. Shi et al., ibid. 18, 3772 (2016)]. Ice II, ice V, and ice XIII have been chosen for this study, since this selection covers many aspects of the polymorphism of ice. That is, ice II is a hydrogen-ordered phase of ice, in contrast to ice Ih, while ice V and ice XIII are a hydrogen-disordered/ordered couple that shares essentially the same oxygen structure and hydrogen-bonded network. For the transmission 2D IR spectroscopy, a novel method had to be developed for the preparation of ultrathin films (1-2 μm) of high-pressure ices with good optical quality. We also simulated 2D IR spectra based on molecular dynamics simulations connected to a vibrational exciton picture. These simulations agree with the experimental results in a semi-quantitative manner for ice II, while the same approach failed for ice V and ice XIII. From the perspective of 2D IR spectroscopy, ice II appears to be more inhomogeneously broadened than ice Ih, despite its hydrogen-order, which we attribute to the fact that ice II is structurally more complex with four distinguishable hydrogen bonds that mix due to exciton coupling. Ice V and ice XIII, on the other hand, behave as expected with the hydrogen-disordered case (ice V) being more inhomogenously broadened. Furthermore, in all hydrogen-ordered forms (ice II and ice XIII), cross peaks could be identified in the anisotropic 2D IR spectrum, whose signs reveal the relative direction of the corresponding excitonic states.

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

Dielectric spectroscopy measurements are carried out in the temperature range from about 100 to 145 K on nominally pure ice V as well as on crystals doped with KOH and with HCl in order to investigate their reorientation dynamics at ambient pressure. The orientational glass transition temperature of pure ice V is detected at 123 K, in agreement with previous indications from calorimetry. KOH doped ice V displays an about 60-fold enhanced hydrogen dynamics and the dipolar relaxation induced by HCl doping is even by a factor of about 40 000 faster than that of the undoped material. The phase transition of HCl doped ice V to ice XIII is accompanied by a significant reorientational slowdown and a pronounced freeze-out of the electrical susceptibility. The results obtained near this transition are discussed in relation to other order/disorder ice pairs such as ice I/XI and ice XII/XIV.

Partially ordered state of ice XV.

Most ice polymorphs have order–disorder “pairs” in terms of hydrogen positions, which contributes to the rich variety of ice polymorphs; in fact, three recently discovered polymorphs— ices XIII, XIV, and XV—are ordered counter forms to already identified disordered phases. Despite the considerable effort to understand order–disorder transition in ice crystals, there is an inconsistency among the various experiments and calculations for ice XV, the ordered counter form of ice VI, i.e., neutron diffraction observations suggest antiferroelectrically ordered structures, which disagree with dielectric measurement and theoretical studies, implying ferroelectrically ordered structures. Here we investigate in-situ neutron diffraction measurements and density functional theory calculations to revisit the structure and stability of ice XV. We find that none of the completely ordered configurations are particular favored; instead, partially ordered states are established as a mixture of ordered domains in disordered ice VI. This scenario in which several kinds of ordered configuration coexist dispels the contradictions in previous studies. It means that the order–disorder pairs in ice polymorphs are not one-to-one correspondent pairs but rather have one-to-n correspondence, where there are n possible configurations at finite temperature.

Calculation of near K edge x-ray absorption spectra and hydrogen bond network in ice XIII under compression

The hydrogen bond network, oxygen K edge x-ray absorption spectra (XAS), and electronic structure of ice XIII under compression have been extensively studied by density functional theory (DFT). We showed that DFT methods yield a ground state consistent with previous neutron scattering experiment and a few low-enthalpy metastable states are likely to coexist from the total enthalpy calculations. Oxygen K edge XAS of four low-enthalpy configurations was studied with the aim to shed light on the local structure in these configurations. We demonstrated that pre-edge of oxygen K edge XAS is a common feature appearing in all these four structures while major spectral differences exist in the main peak area. Therefore, we arrived at the conclusion that the main peak is more sensitive to the local hydrogen bond environment and could be used as an effective tool to distinguish these four configurations. We also found that the pre-edge has main contribution from O 1s-4a1 transitions and its intensity was suppressed by pressure while the main peak is mostly coming from O 1s-2b2 transitions.

Hydrogen bond ordering in ice V and the transition to ice XIII

The proton ordered version of ice V, ice XIII, was recently identified using Raman spectroscopy and neutron diffraction techniques. The transformation, between 108 and 117 K, only occurred in the presence of a small amount of dopant, similar to the proton ordering transition of ice Ih/XI. In this work, we investigate the hydrogen bond fluctuations in ice V and XIII with statistical mechanical techniques that use results from periodic electronic density functional theory calculations as input. We find a number of low-lying hydrogen bond configurations, approximately 20 within 10 K/water above the ground state state configuration, the structure of which agrees with fully ordered ice XIII. Using an analytic theory, graph invariants, we developed effective spin-lattice Hamiltonians governing hydrogen bond fluctuations to perform statistical mechanical calculations for a large simulation cell containing 6048 water molecules. Two models were constructed, one more elaborate than the first, to gauge the robustness of our methods when the unit cell is very complex and a large number of configurations lie close in energy to the ground state. The predicted proton ordering transitions, 62 and 72 K for the two models, are in qualitative agreement with experiment. Occupation probabilities, obtained from our simulations, compare well with values from recent neutron diffraction experiments and help verify our effective Hamiltonians. In both models, we find that a second order phase transition intervenes about 10 K above the transition to ice XIII, but its effect is negligible on the behavior of thermodynamic functions near the transition to ice XIII.

Computing the free energy of molecular solids by the Einstein molecule approach: Ices XIII and XIV, hard-dumbbells and a patchy model of proteins

The recently proposed Einstein molecule approach is extended to compute the free energy of molecular solids. This method is a variant of the Einstein crystal method of Frenkel and Ladd [J. Chem. Phys. 81, 3188 (1984)]. In order to show its applicability, we have computed the free energy of a hard-dumbbell solid, of two recently discovered solid phases of water, namely, ice XIII and ice XIV, where the interactions between water molecules are described by the rigid nonpolarizable TIP4P/2005 model potential, and of several solid phases that are thermodynamically stable for an anisotropic patchy model with octahedral symmetry which mimics proteins. Our calculations show that both the Einstein crystal method and the Einstein molecule approach yield the same results within statistical uncertainty. In addition, we have studied in detail some subtle issues concerning the calculation of the free energy of molecular solids. First, for solids with noncubic symmetry, we have studied the effect of the shape of the simulation box on the free energy. Our results show that the equilibrium shape of the simulation box must be used to compute the free energy in order to avoid the appearance of artificial stress in the system that will result in an increase in the free energy. In complex solids, such as the solid phases of water, another difficulty is related to the choice of the reference structure. As in some cases there is no obvious orientation of the molecules; it is not clear how to generate the reference structure. Our results will show that, as long as the structure is not too far from the equilibrium structure, the calculated free energy is invariant to the reference structure used in the free energy calculations. Finally, the strong size dependence of the free energy of solids is also studied.

A calorimetric study on the low temperature dynamics of doped ice V and its reversible phase transition to hydrogen ordered ice XIII

Doped ice V samples made from solutions containing 0.01 M HCl (DCl), HF (DF), or KOH (KOD) in H(2)O (D(2)O) were slow-cooled from 250 to 77 K at 0.5 GPa. The effect of the dopant on the hydrogen disorder --> order transition and formation of hydrogen ordered ice XIII was studied by differential scanning calorimetry (DSC) with samples recovered at 77 K. DSC scans of acid-doped samples are consistent with a reversible ice XIII <--> ice V phase transition at ambient pressure, showing an endothermic peak on heating due to the hydrogen ordered ice XIII --> disordered ice V phase transition, and an exothermic peak on subsequent cooling due to the ice V --> ice XIII phase transition. The equilibrium temperature (T(o)) for the ice V <--> ice XIII phase transition is 112 K for both HCl doped H(2)O and DCl doped D(2)O. From the maximal enthalpy change of 250 J mol(-1) on the ice XIII --> ice V phase transition and T(o) of 112 K, the change in configurational entropy for the ice XIII --> ice V transition is calculated as 2.23 J mol(-1) K(-1) which is 66% of the Pauling entropy. For HCl, the most effective dopant, the influence of HCl concentration on the formation of ice XIII was determined: on decreasing the concentration of HCl from 0.01 to 0.001 M, its effectiveness is only slightly lowered. However, further HCl decrease to 0.0001 M drastically lowered its effectiveness. HF (DF) doping is less effective in inducing formation of ice XIII than HCl (DCl) doping. On heating at a rate of 5 K min(-1), kinetic unfreezing starts in pure ice V at approximately 132 K, whereas in acid doped ice XIII it starts at about 105 K due to acceleration of reorientation of water molecules. KOH doping does not lead to formation of hydrogen ordered ice XIII, a result which is consistent with our powder neutron diffraction study (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758). We further conjecture whether or not ice XIII has a stable region in the water/ice phase diagram, and on a metastable triple point where ice XIII, ice V and ice II are in equilibrium.

Computer simulation of two new solid phases of water: Ice XIII and ice XIV

NpT Monte Carlo simulations have been performed for two recently discovered solid phases of water which have been denoted as ice XIII and ice XIV C. G. Salzmann et al. [Science311, 1758 (2006)]. Several potential models of water were considered, namely, the traditional SPC/E, TIP4P, and TIP5P and the more recent TIP5P-E, TIP4P-Ew, TIP4P/Ice, and TIP4P/2005 models. Significant differences in density and oxygen-oxygen radial distribution functions are found between the predictions of the SPC/E, TIP5P, and the models of the TIP4P family. The models TIP4P/Ice and TIP4P/2005 provide the best estimates of the density.

The Preparation and Structures of Hydrogen Ordered Phases of Ice

Two hydrogen ordered phases of ice were prepared by cooling the hydrogen disordered ices V and XII under pressure. Previous attempts to unlock the geometrical frustration in hydrogen-bonded structures have focused on doping with potassium hydroxide and have had success in partially increasing the hydrogen ordering in hexagonal ice I (ice Ih). By doping ices V and XII with hydrochloric acid, we have prepared ice XIII and ice XIV, and we analyzed their structures by powder neutron diffraction. The use of hydrogen chloride to release geometrical frustration opens up the possibility of completing the phase diagram of ice.

Raman spectroscopic study of hydrogen ordered ice XIII and of its reversible phase transition to disordered ice V

Raman spectra of recovered ordered H(2)O (D(2)O) ice XIII doped with 0.01 M HCl (DCl) recorded in vacuo at 80 K are reported in the range 3600-200 cm(-1). The bands are assigned to the various types of modes on the basis of isotope ratios. On thermal cycling between 80 and 120 K, the reversible phase transition to disordered ice V is observed. The remarkable effect of HCl (DCl) on orientational ordering in ice V and its phase transition to ordered ice XIII, first reported in a powder neutron diffraction study of DCl doped D(2)O ice V (C. G. Salzmann, P. G. Radaelli, A. Hallbrucker, E. Mayer, J. L. Finney, Science, 2006, 311, 1758), is demonstrated by Raman spectroscopy and discussed. The dopants KOH and HF have only a minor effect on hydrogen ordering in ice V, as shown by the Raman spectra.

Formation of Quasi Two-dimensional Bilayer Ice in Hydrophobic Slits: A Possible Candidate for Ice XIII?

We performed molecular dynamics simulations of water confined to hydrophobic slit nanopores. Two five-site potential models of water were employed: the ST2 model and the TIP5P model. The simulations confirm our previous simulation results on basis of the four-site TIP4P model of water, that is, upon cooling the confined liquid water may undergo a first-order phase transition to either a bilayer crystalline ice phase or to a bilayer amorphous ice. The selection of the bilayer crystalline phase occurs at the constant normal pressure condition whereas the selection of the bilayer amorphous ice phase is likely to occur at the fixed pore-width condition. This computer-simulation generated ice form, if confirmed by crystallographic or spectroscopic experiments, may be a candidate for “ice XIII”, provided that purely quasi two-dimensional ice forms (metastable in vacuum) can be viewed as a stand-alone solid phase of ice.