Elastic properties of D<Subscript>2</Subscript>O ices in solid-state amorphization and transformations between amorphous phases

Nonequilibrium phase transformations in D₂O ices, including the solid-state amorphization of ice 1h (1h-hda) and the heating-induced transition cascade hda-lda-1c-1h from high-density amorphous (hda) ice to low-density amorphous (lda) ice followed by crystallization in cubic ice 1c and phase transition to ordinary hexagonal ice 1h, were studied using an ultrasonic technique. It has been shown that, as in H₂O ice, the softening of a crystal lattice or an amorphous network precedes nonequilibrium transformations. However, noticeable isotopic differences in the behavior of the elastic properties of H₂O and D₂O, in particular, their 1h and hda modifications, call for a more detailed study of the structural features of these H₂O and D₂O phases.     

Thermoluminescence study of the amorphisation of hexagonal ice by irradiation at 77 K

This paper reports on a thermoluminescence study of D₂O ice I_h. A sample of hexagonal (I_h) ice is irradiated by a 100 MeV X-ray source at 77 K. The emission spectrum that is measured immediately after the end of the irradiation process has the thermoluminescent behaviour of amorphous ice. The kinetic transition is followed to the stable form, taking place at 85 K. The relaxation time of the transition is of the order of 5 minutes. It is concluded that, due to irradiation, a few outer layers of ice I_h are converted to the low-density amorphous form of ice, which then converts to cubic ice. Although complex to quantify, thermoluminescence appears to be, in the present study, particularly sensitive to the time evolution of irradiated samples.     

Calorimetric study of a phase transition in D2O ice Ih doped with KOD: Ice XI

D₂O ice Ih doped with KOD was found by calorimetry to undergo a phase transition at 76 K. The enthalpy and entropy of the phase transition depended in their magnitude on the annealing of the sample. The largest values obtained were ΔH = 155 J mol⁻¹ and δS = 2.06 J K⁻¹ mol⁻¹. The phase transition removed 64% of the residual entropy. Mechanisms of the isotope effect were discussed to explain the difference in the transition temperatures of the D₂O and H₂O ices and compared with the experiment. The pressure coefficient of the transition temperature was calculated by the use of the Clapeyron-Clausius equation and recent data on the molar volume of the new phase. The name ice XI is proposed to designate the ordered phase of ice Ih.     

Crossover between the thermodynamic and nonequilibrium scenarios of structural transformations of H<Subscript>2</Subscript>O I<Emphasis Type="Italic">h</Emphasis> ice during compression

A detailed investigation of different scenarios of structural transformations of H₂O Ih ice during compression to a pressure of 2 GPa in the temperature range from 77 to 200 K is performed. In the range of temperatures and pressures being treated, detailed data are obtained for the density and the shear modulus for different phases of ice including the hda, IX, and XII phases. The experimentally obtained correlations for the density and ultrasonic velocities, with due regard for the available data of structural investigations, are used to identify the transformation sequences Ih→hda (below 135 K), Ih→II→VI (above 165 K), and Ih→IX→VI (from 155 to 180 K). In the vicinity of the crystallization temperature of amorphous ice, i.e., at about 140 K, an anomalous transformation pattern is observed, which is interpreted as predominantly the Ih→XII phase transition. The temperature crossover is discussed between the mode of solid-phase amorphization (Ih→hda) and crystal-crystal transitions, as well as the metastable nature of IX ice and the mechanism of solid-phase amorphization.     

Molecular Structures of H2X and D2X(X=0, S,Se, Te)

There are two possible configurations for H₂O, linear(D_∞h) or bent(C_2v). For a C_2v′, the three bands ν_1′ ν₂ and ν₃ should appear in both Raman and infrared. For a D_∞h. however, the ν₁, band should appear in only Raman and the ν₂ and ν₃ bands, in only infrared, that is, a principle of mutual exclusion of Raman and infrared should hold. The present author concludes that H₂X and D₂X(X=O, S, Se, Te) have a linear D_∞h. structure, since the obtained spectra show mutual exclusion of Raman and infrared.     

Comparative analysis of the v(OD) and 2v 3(H2O) spectral bands of H2O-D2O system under isobaric heating conditions

The results of an investigation of the influence of isobaric heating on distribution of hydrogen bonds in the H₂O-D₂O system on the basis of comparative complex analysis of the v(OD) and 2v ₃(H₂O) spectral bands are presented. In the case of analysis of the band assigned to the 2v ₃(H₂O) overtone, the possibilities of obtaining more detailed information on the influence of external factors on the formation of local water structure widen significantly. In particular, there are noticeable differences in the quality of the obtainable data for these bands, which are especially manifested in their low-frequency regions, which are determined by the presence of strong hydrogen bonds characteristic of H-bonded high order water n-mers.     

Crystal-field analysis for d ions at D4h symmetry sites: Electronic states in trans-NiCl2(H2O)4 complex

The polarized absorption spectra of trans-NiCl₂(H₂O)₄ complex were measured by Bussière et al. [Coord. Chem. Rev. 219-221 (2001) 509-543] at low-temperature. Using the experimental spectroscopic data, semiempirical calculations of the crystal-field levels of trans-NiCl₂(H₂O)₄ chromophore are carried out, based on the Racah theory. We used idealized D_4h point group symmetry to analyse the observed crystalline-field splitting of this chromophore. As a result, Racah and crystal-field parameters have been reliably obtained. A good agreement between the theoretical and experimental energy levels of trans-NiCl₂(H₂O)₄ complex has been obtained. The region of ³T_1g/¹E_g(O_h) bands is of great interest and it is useful to use the tetragonal symmetry to understand the features of this spectral region.     

Isotopic effects in the establishment of thermal equilibrium of stationary H2- and D2-glow plasmas

In stationary glow plasmas, thermal equilibrium of the electron gas with the neutral gas is established, if, with increasing gas pressure, the diffusion lifetime of plasma electrons becomes high enough. In D₂-plasmas, thermal equilibrium sets in at higher pressures than in H₂. Equal electron temperatures are measured in H₂- and D₂-glows, if the corresponding gas pressures are in the ratiop d ₂/P h ₂=1.22. This isotopic effect of electron temperature and of thermal equilibrium is compared with calculations of the Boltzmann equation, taking into account the influence of ambipolar diffusion on the electron velocity distribution. There is a good agreement between measurement and theory.     

X-Ray photoelectron study of the reaction of water with cerium

The interaction of D₂ O with a polycrystalline cerium surface, successfully cleaned by heavy Ar⁺ bombardment and annealing, was studied at 120 were observed at BE 530.3 (Ce₂O₃) and 532.7eV (adsorbed OD). When clean Ce at 120 K was exposed to D₂ O, the O(1s) spectra were initial eV (adsorbed D₂ O). For exposures greater than 10 Langmuir (L), a multilayer of ice grows and the O(1s) spectra become dominated by a peak at 5The results of interaction with D₂ O are compared with oxidation by O₂. The significant differences are: (1) the absence of Ce(IV) when oxidati relatively small extent of oxidation that occurs when Ce is exposed to D₂ O at 120 K, and (3) the larger chemical-shift of the Ce(III)-derived specThe XPS studies of the interaction of D₂ O with Ce reported here may be summarized as follows:(1) Exposure at 300 K gives rise to O(1s) features characteristic of oxide and hydroxide, while the Ce(3d) spectra indicate Ce(III), but no CE((2) Exposure at 120 K gives O(1s) features characteristic of adsorbed OD, chemisorbed D₂ O, a multilayer of ice, and a small amount of oxide. T are characteristic of clean Ce except for slight broadening.(3) Exposure at 120 K followed by warming to 240 and 300 K gives spectra characteristic of hydroxide and oxide surface-species. Between 240 and 300 K, O(1s) intensity.(4) At 300 K, a relatively thick layer of oxide forms, and after an exposure of 50 L the features characteristic of metallic Ce are no longer observabl(5) As compared to the case for O₂, exposure to D₂ O gives rise to different satellite-splittings in the Ce(3d) spectra, suggesting that di formed in the two cases.(6) The spectra observed for Ce exposed to D₂ O are in excellent accord with those found for the heavier lanthanides [4].     

High-Resolution IR Spectroscopy of the N2O-H2O and N2O-D2O van der Waals Complexes

We report high-resolution infrared vibrational-rotational spectra of the weakly bound complexes N₂O-H₂O and N₂O-D₂O in the higher frequency N₂O stretching mode region (ν₃=2223.756693(124) cm⁻¹). The measurements were carried out using a free jet expansion in combination with a lead salt diode laser spectrometer. Rotational constants, quartic centrifugal distortion constants, and band origins have been derived for both isotopomers. The geometrical structure is determined using isotopic substitution. The deduced structure shows evidence for a second hydrogen bond interaction within the complex. The nonrigidity of the complexes gives rise to an internal rotation of the water molecule around its own C_2v symmetry axis. For N₂O-H₂O, a tunneling splitting arising from this internal motion has been observed in the spectra. According to symmetry considerations, the observed splitting in the spectrum of N₂O-H₂O corresponds to the difference between the tunneling frequencies in the ground and vibrationally excited states.     

Penning ionization electron spectroscopy of H2O,D2O,H2S and SO2

Electron energy peak shifts and peak shapes were determined in the ionization of H₂O, D₂O, H₂S and SO₂ by Ne(³P₂) and He(2¹S, 2³S) metastable atoms. The shifts are large, especially in ionization of H₂O and D₂O into the ionic ground state and are probably mostly due to chemical interaction during the collision.In a previous paper the electron energy distribution curves for ionization of CO, HCl, HBr, N₂O, NO₂, CO₂, COS and CS₂ by helium, neon and argon metastables and the characteristics of this ionization were described¹. In this paper the series of triatomic molecules was extended to the molecules H₂O, D₂O, H₂S and SO₂. Because all these molecules have considerable dipole moments it could be expected that the peak shifts might be enhanced as compared with other triatomic molecules.     

Vibrationally assisted diffusion of H2O and D2O on Pd(1 1 1)

The adsorption and diffusion of isolated H₂O and D₂O molecules on Pd(1 1 1) were studied using scanning tunneling microscopy at low temperature (∼40 K). At low tunneling voltage the diffusion is thermally activated. The diffusion rate is enhanced by several orders of magnitude when the tunneling electron has enough energy to excite the vibrational “scissor” mode of the molecule. An isotope effect was observed in the threshold voltage for electron-assisted diffusion of H₂O and D₂O.     

Vibration properties of low-fraction hydrogen in deuterium ices

Inelastic incoherent neutron scattering spectra of D2O high-density amorphous （hda） ice, ice-Ⅷ and ice-Ⅱ mixed with small amount of H2O （（5%） have been measured recently on high-energy transfer spectrometer at Rutherford Appleton Laboratory （UK）. The hydrogen atom on D2O ice lattices has three distinguished vibrational modes, two bending at low frequencies and one stretching at high frequencies, and their frequencies are slightly different for different phases of ice. It was found that the lower one of the bending modes is located at -95 meⅤ for hda-ice, at -95 meⅤ for ice-Ⅷ and at -96 meⅤ for ice-Ⅱ and they are all lower than the value of 104 meⅤ for ice-Ih. It was also measured that the O-D and O-H covalent bond stretching modes of ice-Ⅷ are at -315 and -425 meⅤ, ice-Ⅱ at 307 and -415 meⅤ, hda-ice at 312 and -418 meⅤ, respectively. They are significantly higher than the values of ice-Ih at -299 and -406 meⅤ, respectively.     

Ion-induced molecular ejection from D2O ice

Studies of molecules ejected from water ice by fast ions provide insight into the electronic relaxation processes and subsequent chemistry occurring in ice at very low temperatures. The ion-induced ejection of D₂O, D₂, and O₂ molecules from thin films of D₂O ice has been measured as a function of the fluence of incident MeV ions at temperatures between 10 and 140 K. For a given beam current, the O₂ yield exhibits initial transients which are slow compared with the prompt ejection of D₂O. We interpret these results as due to the build-up of O₂ in the films following fragmentation of D₂O molecules by incident ions. The fragmens re-form into new molecular species which diffuse to and escape from the surface, aided by subsequent bombardment. The D₂ transient has a prompt component, which we postulate is due to rapid formation during electronic recombination near the surface. A slow component of the D₂ transient is also observed, which may arise through a two-step process similar to that of O₂. Time-of-flight energy spectra of the ejected D₂O molecules have also been measured. Incident ion masses and energies range from those for which nuclear elastic energy deposition dominates (50 keV argon) to those for which electronic energy deposition dominates (1.5 MeV helium). The spectra cannot be described by models typically employed for the sputtering of metals. For instance, the spectra do not have maxima characteristic of the sublimation energy of the solid. In addition, the sputtering yield in the high energy part of the ejection spectrum of D₂O is too large to arise from nuclear elastic energy deposition. It must result instead from relatively energetic non-radiative relaxation of electronic excitation. For incident MeV ions that deposit their energy predominantly in electronic excitation, the low energy part of the D₂O ejection spectrum is greatly enhanced, indicative of a weakly antibinding region formed along an incident particle track. Enhanced ion yields are also found in the collision cascade region which are attributed to electronic processes.     

Coincidence of rotational energy of H<Subscript>2</Subscript>O ortho-para molecules and translation energy near specific temperatures in water and ice

A hypothesis of the quantum nature of the specific temperatures T _s of water and ice, whose values is not random, was formulated. It was found that the quantum energy hΩ _mn of closely located rotational transitions in the ortho and para spin isomers of H₂O molecules coincides with the translation energy kT near the well-known specific temperatures T _s in ice and water. On the basis of this fact it was suggested that ortho-para conversion occurs at temperatures close to T _s upon inelastic collisions and resonance energy exchange kT _s ↔ hΩ _mn in the rotation-translation-rotation (RTR) processes. Such conversion can induce rearrangement of the H-bond set structure and repacking of H₂O molecules. The coincidence kT _s ≈ hΩ _mn was checked for ice and water at 12 known T _s, as well as for heavy water D₂O near T _s = 11.2°C (maximum density) and −140°C (glassy transition). The previously observe strong deformation of the OH Raman band near T _s = 4, 19, 36, and 76°C (maximum density, maximum surface tension, minimum heat capacity, and maximum speed of sound, respectively) was interpreted as a manifestation of the water structure rearrangement induced by H₂O ortho-para conversion.     

Raman study of (NH4)2CuCl4·2H2O—I: Dynamics and structure in low temperature phase

We report the results of a Raman scattering study of (NH₄)₂CuCl₄2H₂O at 300, 205 and 100°K, in order to elucidate the dynamics and phase transition in this double salt. A group theoretical calculation of the symmetry vectors, in the high temperature phase (D_4h¹⁴), is made and the various modes are identified. The deuterated compound (ND₄)₂CuCl₄·2D₂O has also been investigated to help in identifying the modes involving motion of the ammonium ions and water molecules. Through a careful analysis of the spectra at 100°K, the space group in the low temperature phase has been established as D_2d³. The important consequence of this result is that this leads to parallel spatial ordering of ammonium tetrahedra in this compound in the low temperature phase.     

The 2ν2 and ν1 bands of HD16O

The 2ν₂ and ν₁ bands of HDO lying in the region 2235–3115 cm^?1 were analyzed using Fourier transform spectra of “pure” D₂O and of H₂OD₂O mixtures. From this analysis, an extended and precise set of rotational levels belonging to the (000), (020), and (100) vibrational states was derived. Using the (000) levels together with the existing microwave data as input in a least-squares fit, it was possible to obtain reliable rotational constants for the ground state of the HDO molecule.     

The Rotational Spectra of H2CCSi and H2C4Si

The microwave rotational spectra of two singlet chains H₂CCSi and H₂C₄Si, have been observed in a pulsed supersonic molecular beam by Fourier transform microwave spectroscopy. Following detection of the singly substituted rare isotopic species and D₂CCSi, an experimental structure (r₀) has been determined to high accuracy for H₂CCSi by isotopic substitution. In addition, the rotational transitions of the ²⁹Si and the two ¹³C isotopic species of H₂CCSi exhibit nuclear spin-rotation hyperfine structure. The component of the spin-rotation tensor along the a-inertial axis is abnormally large for each of these isotopic species, especially for that with ²⁹Si, where the magnitude of C_aa is in excess of 700 kHz.     

Velocity dependence of the chemi-ionization of H2O and D2O on impact of 21S and 23S helium atoms

The velocity dependence for the ionization of H₂O and D₂O to form H₂O⁺ and D₂O⁺ in collisions with both 2³S and 2¹S metastable helium atoms has been measured in a crossed molecular beam apparatus using a mechanical velocity-selector on the metastable beam. The cross-sections are found to be proportional to the —n power of the relative collision energy, with n ? 0.4 for both metastable atoms in both gases. The branching ratios H₂O⁺/OH⁺ and D₂O⁺/OD⁺ were both found to be 4.3 for both metastable helium atoms, and to be independent of the relative collision energy.