scholarly journals Anomalous hydrogen dynamics of the ice VII–VIII transition revealed by high-pressure neutron diffraction

2020 ◽  
Vol 117 (12) ◽  
pp. 6356-6361 ◽  
Author(s):  
Kazuki Komatsu ◽  
Stefan Klotz ◽  
Shinichi Machida ◽  
Asami Sano-Furukawa ◽  
Takanori Hattori ◽  
...  
Keyword(s):  
Neutron Diffraction ◽  
Translational Motion ◽  
Simultaneous Increase ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Oxygen Sublattice ◽  
X Ray ◽  
Slowing Down ◽  
Solid Phases ◽  
Two Phases

Above 2 GPa the phase diagram of water simplifies considerably and exhibits only two solid phases up to 60 GPa, ice VII and ice VIII. The two phases are related to each other by hydrogen ordering, with the oxygen sublattice being essentially the same. Here we present neutron diffraction data to 15 GPa which reveal that the rate of hydrogen ordering at the ice VII–VIII transition decreases strongly with pressure to reach timescales of minutes at 10 GPa. Surprisingly, the ordering process becomes more rapid again upon further compression. We show that such an unusual change in transition rate can be explained by a slowing down of the rotational dynamics of water molecules with a simultaneous increase of translational motion of hydrogen under pressure, as previously suspected. The observed cross-over in the hydrogen dynamics in ice is likely the origin of various hitherto unexplained anomalies of ice VII in the 10–15 GPa range reported by Raman spectroscopy, X-ray diffraction, and proton conductivity.

Opening and Narrowing of the Water H—O—H Angle by Hydrogen-Bonding Effects: Re-inspection of Neutron Diffraction Data

1998 ◽  
Vol 54 (4) ◽  
pp. 464-470 ◽  
Author(s):  
T. Steiner
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Neutron Diffraction ◽  
Diffraction Data ◽  
Water Molecules ◽  
Hydroxyl Groups ◽  
Secondary Effects ◽  
X Ray Diffraction ◽  
X Ray ◽  
Sample Average

For 71 water molecules donating two Ow—H...O hydrogen bonds, the correlation of the covalent H—O—H angle and the O...Ow...O angle is inspected from 49 well refined organic and organometallic neutron diffraction crystal structures. Compared to sample average, the water angle is opened for large and narrowed for small O...Ow...O angles. Notably, the H—O—H angle is widened compared with the gas phase value even for small O...Ow...O. Related behavior is observed for chloride anion acceptors. The correlation exhibits a considerable scatter which should not be interpreted as experimental inaccuracies, but as secondary effects. Possible secondary effects are multi-center hydrogen bonding and effects of coordination to the water O atom. In a comparative test, low-temperature X-ray diffraction data were shown to be completely unsuitable for this type of analysis. The dependence of the C—O—H angle on the C—O...O angle in hydrogen bonds donated by hydroxyl groups in carbohydrates is also shown.

Structure, Charge and Spin Density in Na2Ni(CN)4.3H2O at 295 and 30 K

1998 ◽  
Vol 54 (5) ◽  
pp. 600-612 ◽  
Author(s):  
H. Ptasiewicz-Bak ◽  
I. Olovsson ◽  
G. J. McIntyre
Keyword(s):  
Neutron Diffraction ◽  
Crystal Field ◽  
Spin Density ◽  
Lone Pair ◽  
Water Molecules ◽  
Sodium Ions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Deformation Density ◽  
The Individual

The earlier reported structure of the title compound, disodium tetracyanonickelate(II) trihydrate, Na2Ni(CN)4.3H2O, has been found to be incorrect and has now been redetermined. The charge distribution has been determined by multipole refinements against single-crystal X-ray diffraction data. In the refinement based on 30 K data a comparison was made between the results obtained using hydrogen positions and displacement parameters from X-ray diffraction with those using the values determined by neutron diffraction. The spin density was investigated by polarized neutron diffraction at 1.6 K. Crystal data: at T = 30 K: a = 7.278 (4), b = 8.856 (5), c = 15.131 (8) Å, α = 89.32 (5), β = 87.39 (4), γ = 83.61 (4)°; at 295 K: a = 7.392 (4), b = 8.895 (4), c = 15.115 (8)  Å, α = 89.12 (2), β = 87.46 (2), γ = 84.54 (2)°. The structure contains practically square planar Ni(CN)_4^{2-} ions, which are stacked on top of each other in almost linear chains along the a direction. The separation between the Ni(CN)_4^{2-} planes is rather large, with Ni—Ni distances around 3.7 Å. The six crystallographically independent water molecules are each coordinated to two sodium ions, approximately in the tetrahedral (lone-pair) directions, and the polarizing influence of these sodium ions also appears to be reflected in the deformation density in the lone-pair plane. The charge density based on the deformation functions of all atoms in the structure is compared with the individual densities calculated from the deformation functions of only nickel or the separate water molecules. In this way the effects of simple superposition of the individual densities have been studied. In the planar Ni(CN)_4^{2-} ion the individual deformation density of nickel is in qualitative agreement with that expected from crystal-field theory. As the repulsion from the electrons is much weaker perpendicular to the Ni(CN)_4^{2-} plane than within this plane, the deformation density is considerably larger in the perpendicular direction. However, the largest maxima in the individual deformation density around nickel are not found precisely in the planes defined by nickel and the four cyanide ligands or in the perpendicular direction just mentioned, which illustrates that it is necessary to consider the crystal field due to the whole crystalline environment.

The water molecules in CuSO 4 .5H 2 O

1962 ◽  
Vol 266 (1324) ◽  
pp. 95-108 ◽  
Keyword(s):  
Hydrogen Bonds ◽  
Neutron Diffraction ◽  
Single Crystals ◽  
Water Molecules ◽  
X Ray Diffraction ◽  
Neutron Data ◽  
X Ray ◽  
Atomic Nuclei ◽  
Different Temperatures ◽  
Molecular Rotations

Single crystals of fully hydrated copper sulphate have been studied by neutron diffraction and the measurements have been used to construct projections of the neutron-scattering density, due to the atomic nuclei, on the three crystallographic axial planes. These provide full details of the shape and environment of the water molecules and of the hydrogen bonds which link together the atoms in the structure, which was originally proposed by Beevers & Lipson as a result of X -ray diffraction work. It is found that the H—O—H angles for all the water molecules are within a degree or two of the tetrahedral value and the hydrogen bonds have to be bent by up to 26° in order to accommodate them. Corresponding measurements have been made at a series of five different temperatures between 20 and 90°C in order to test a suggestion that molecular rotations of the water molecules occurred before the onset of dehydration: the neutron data refute this suggestion.

Phase Transitions in Perovskite Phases of Strontium Silicoantimonates

2016 ◽  
Vol 845 ◽  
pp. 34-37 ◽  
Author(s):  
Yulia N. Kuryleva ◽  
Olga A. Chalaya ◽  
D.A. Zakharyevich
Keyword(s):  
Thermal Analysis ◽  
Phase Transitions ◽  
Room Temperature ◽  
Water Molecules ◽  
Chemical Transformations ◽  
X Ray Diffraction ◽  
Oxygen Sublattice ◽  
Structural Water ◽  
X Ray ◽  
The Third

The paper presents the results of the study of phase transitions in the system Sr-Sb-Si-O by means of X-ray diffraction, thermal analysis, dielectric spectroscopy. Four effects are observed in the interval from room temperature to 800°C. The first and last are chemical transformations due to dehydration and loss of oxygen, respectively. The second is a transition from tetragonal to cubic perovskite structure, and the third is disordering transition in oxygen sublattice possibly due to the desorption of structural water molecules

scholarly journals Evaluation of models determined by neutron diffraction and proposed improvements to their validation and deposition

2018 ◽  
Vol 74 (8) ◽  
pp. 800-813 ◽  
Author(s):  
Dorothee Liebschner ◽  
Pavel V. Afonine ◽  
Nigel W. Moriarty ◽  
Paul Langan ◽  
Paul D. Adams
Keyword(s):  
Neutron Diffraction ◽  
Current Model ◽  
Data Bank ◽  
Water Molecules ◽  
Macromolecular Crystallography ◽  
X Ray Diffraction ◽  
X Ray ◽  
Manual Intervention ◽  
Data Files

The Protein Data Bank (PDB) contains a growing number of models that have been determined using neutron diffraction or a hybrid method that combines X-ray and neutron diffraction. The advantage of neutron diffraction experiments is that the positions of all atoms can be determined, including H atoms, which are hardly detectable by X-ray diffraction. This allows the determination of protonation states and the assignment of H atoms to water molecules. Because neutrons are scattered differently by hydrogen and its isotope deuterium, neutron diffraction in combination with H/D exchange can provide information on accessibility, dynamics and chemical lability. In this study, the deposited data, models and model-to-data fit for all PDB entries that used neutron diffraction as the source of experimental data have been analysed. In many cases, the reported R work and R free values were not reproducible. In such cases, the model and data files were analysed to identify the reasons for this mismatch. The issues responsible for the discrepancies are summarized and explained. The analysis unveiled limitations to the annotation, deposition and validation of models and data, and a lack of community-wide accepted standards for the description of neutron models and data, as well as deficiencies in current model refinement tools. Most of the issues identified concern the handling of H atoms. Since the primary use of neutron macromolecular crystallography is to locate and directly visualize H atoms, it is important to address these issues, so that the deposited neutron models allow the retrieval of the maximum amount of information with the smallest effort of manual intervention. A path forward to improving the annotation, validation and deposition of neutron models and hybrid X-ray and neutron models is suggested.

Defect structures of Nb1+αS2 sulfidation scales

1992 ◽  
Vol 50 (1) ◽  
pp. 38-39
Author(s):  
Chuxin Zhou ◽  
L. W. Hobbs
Keyword(s):  
Stacking Faults ◽  
Rhombohedral Structure ◽  
Stacking Sequence ◽  
Defect Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Plane Normal ◽  
Lower Case ◽  
Sulfur Layer ◽  
Two Phases

One of the major purposes in the present work is to study the high temperature sulfidation properties of Nb in severe sulfidizing environments. Kinetically, the sulfidation rate of Nb is satisfactorily slow, but the microstructures and non-stoichiometry of Nb1+αS2 challenge conventional oxidation/sulfidation theory and defect models of non-stoichiometric compounds. This challenge reflects our limited knowledge of the dependence of kinetics and atomic migration processes in solid state materials on their defect structures.Figure 1 shows a high resolution image of a platelet from the middle portion of the Nb1+αS2 scale. A thin lamellar heterogeneity (about 5nm) is observed. From X-ray diffraction results, we have shown that Nb1+αS2 scale is principally rhombohedral structure, but 2H-NbS2 can result locally due to stacking faults, because the only difference between these 2H and 3R phases is variation in the stacking sequence along the c axis. Following an ABC notation, we use capital letters A, B and C to represent the sulfur layer, and lower case letters a, b and c to refer to Nb layers. For example, the stacking sequence of 2H phase is AbACbCA, which is a ∼12Å period along the c axis; the stacking sequence of 3R phase is AbABcBCaCA to form an ∼18Å period along the c axis. Intergrowth of these two phases can take place at stacking faults or by a shear in the basal plane normal to the c axis.

Texture measurements in Al2O3 using BEKP

1994 ◽  
Vol 52 ◽  
pp. 608-609
Author(s):  
M. D. Vaudin ◽  
J. P. Cline
Keyword(s):  
Neutron Diffraction ◽  
Rapid Method ◽  
Crystallographic Orientation ◽  
Specimen Surface ◽  
X Ray Diffraction ◽  
Anisotropic Crystal ◽  
X Ray ◽  
Verification Method ◽  
Crystal Properties ◽  
Backscattered Electron

The study of preferred crystallographic orientation (texture) in ceramics is assuming greater importance as their anisotropic crystal properties are being used to advantage in an increasing number of applications. The quantification of texture by a reliable and rapid method is required. Analysis of backscattered electron Kikuchi patterns (BEKPs) can be used to provide the crystallographic orientation of as many grains as time and resources allow. The technique is relatively slow, particularly for noncubic materials, but the data are more accurate than any comparable technique when a sufficient number of grains are analyzed. Thus, BEKP is well-suited as a verification method for data obtained in faster ways, such as x-ray or neutron diffraction. We have compared texture data obtained using BEKP, x-ray diffraction and neutron diffraction. Alumina specimens displaying differing levels of axisymmetric (0001) texture normal to the specimen surface were investigated.BEKP patterns were obtained from about a hundred grains selected at random in each specimen.

Structural Study of a new Compound Based on Acid 1,4-Cyclohexanedicarboxylic (1,4-CDC)

2010 ◽  
Vol 6 (1) ◽  
pp. 891-896
Author(s):  
Manel Halouani ◽  
M. Dammak ◽  
N. Audebrand ◽  
L. Ktari
Keyword(s):  
Aqueous Solution ◽  
Water Molecules ◽  
Carboxyl Group ◽  
X Ray Diffraction ◽  
Compound I ◽  
Unit Cell Parameters ◽  
Monoclinic System ◽  
X Ray ◽  
Cell Parameters ◽  
Cyclohexanedicarboxylic Acid

One nickel 1,4-cyclohexanedicarboxylate coordination polymers, Ni2 [(O10C6H4)(COO)2].2H2O  (I), was hydrothermally synthesized from an aqueous solution of Ni (NO3)2.6H2O, (1,4-CDC) (1,4-CDC = 1,4-cyclohexanedicarboxylic acid) and tetramethylammonium nitrate. Compound (I) crystallizes in the monoclinic system with the C2/m space group. The unit cell parameters are a = 20.1160 (16) Å, b = 9.9387 (10) Å, c = 6.3672 (6) Å, β = 97.007 (3) (°), V= 1263.5 (2) (Å3) and Dx= 1.751g/cm3. The refinement converged into R= 0.036 and RW = 0.092. The structure, determined by single crystal X-ray diffraction, consists of two nickel atoms Ni (1) and Ni (2). Lots of ways of which is surrounded by six oxygen atoms, a carboxyl group and two water molecules.

scholarly journals X-ray and Neutron Study on the Structure of Hydrous SiO2 Glass up to 10 GPa

Minerals ◽  
2020 ◽  
Vol 10 (1) ◽  
pp. 84 ◽  
Author(s):  
Satoru Urakawa ◽  
Toru Inoue ◽  
Takanori Hattori ◽  
Asami Sano-Furukawa ◽  
Shinji Kohara ◽  
...  
Keyword(s):  
Oxide Glasses ◽  
Void Space ◽  
X Ray Diffraction ◽  
Amorphous Sio2 ◽  
Sio2 Glass ◽  
X Ray ◽  
X Ray Scattering ◽  
Medium Range ◽  
Two Phases ◽  
A Minor

The structure of hydrous amorphous SiO2 is fundamental in order to investigate the effects of water on the physicochemical properties of oxide glasses and magma. The hydrous SiO2 glass with 13 wt.% D2O was synthesized under high-pressure and high-temperature conditions and its structure was investigated by small angle X-ray scattering, X-ray diffraction, and neutron diffraction experiments at pressures of up to 10 GPa and room temperature. This hydrous glass is separated into two phases: a major phase rich in SiO2 and a minor phase rich in D2O molecules distributed as small domains with dimensions of less than 100 Å. Medium-range order of the hydrous glass shrinks compared to the anhydrous SiO2 glass by disruption of SiO4 linkage due to the formation of Si–OD deuterioxyl, while the response of its structure to pressure is almost the same as that of the anhydrous SiO2 glass. Most of D2O molecules are in the small domains and hardly penetrate into the void space in the ring consisting of SiO4 tetrahedra.

scholarly journals ZnOTe Compounds Grown by DC-Magnetron Co-Sputtering

Coatings ◽  
2021 ◽  
Vol 11 (5) ◽  
pp. 570
Author(s):  
Olga Sánchez ◽  
Manuel Hernández-Vélez
Keyword(s):  
Molar Fraction ◽  
Variable Parameter ◽  
Point Of View ◽  
X Ray Diffraction ◽  
X Ray ◽  
Sample Series ◽  
Solid Phases ◽  
The One ◽  
High Bulk ◽  
Substrate Sample

ZnOTe compounds were grown by DC magnetron cosputtering from pure Tellurium (Te) and Zinc (Zn) cathodes in O2/Ar atmosphere. The applied power on the Zn target was constant equal to 100 W, while the one applied on the Te target took two values, i.e., 5 W and 10 W. Thus, two sample series were obtained in which the variable parameter was the distance from the Te targets to the substrate. Sample compositions were determined by Rutherford Backscattering Spectroscopy (RBS) experiments. Structural analysis was done using X-Ray diffraction (XRD) spectrometry and the growth of the hexagonal w-ZnO phase was identified in the XRD spectra. RBS results showed high bulk homogeneity of the samples forming ZnOTe alloys, with variable Te molar fraction (MF) ranging from 0.48–0.6% and from 1.9–3.1% for the sample series obtained at 5 W and 10 W, respectively. The results reflect great differences between the two sample series, particularly from the structural and optical point of view. These experiments point to the possibility of Te doping ZnO with the permanence of intrinsic defects, as well as the possibility of the formation of other Te solid phases when its content increases. The results and appreciable variations in the band gap transitions were detected from Photoluminescence (PL) measurements.

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