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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 5751-5760 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Neutron diffraction, in conjuction with substitution of deuterium (D) for hydrogen (H), has been used to determine the structure of interlayer water in sodium- and nickel-substituted vermiculites. We have measured the intensities of the (00l) Bragg reflections as a function of relative humidity and H/D content, up to l=30. Difference analysis has then been used to obtain separate density profiles, ρ(z), for both the hydrogen atoms and the oxygen atoms plus the clay sheets. Ni–vermiculite was studied at 84% relative humidity, while Na–vermiculite was studied at both 88% and 30% relative humidity. At these values the layer spacings are 14.40, 14.96, and 11.78 A(ring), respectively. We find that each interlayer nickel ion is coordinated octahedrally to 6.0 water molecules. All of these water molecules are oriented to form a strong hydrogen bond to the adjacent clay surface. We also find that extra water is located close to the clay layers. This additional water is situated within the hexagonal rings of SiO4 and AlO−4 tetrahedra, which comprise the clay surfaces. In the 14.96 A(ring) phase of Na–vermiculite there are an average of 4.9 interlayer water molecules per cation. About half of these water molecules are oriented to form a hydrogen bond to one of the clay surfaces. Additional water is found close to the clay surface, occupying the same hexagonal ring sites as in 14.40 A(ring) Ni–vermiculite. In the 11.78 A(ring) phase of Na–vermiculite there are an average of 2.1 water molecules per interlayer cation. The oxygen atoms of these interlayer water molecules are found close to halfway between the layers, while the hydrogen atoms are directed towards one of the adjacent clay sheets.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 1320-1331 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Neutron diffraction with hydrogen/deuterium isotope substitution is used to investigate the structure of water in concentrated dimethyl sulphoxide (DMSO) aqueous solutions. Partial structure factors and pair correlation functions involving the hydrogen atom on the water molecule are determined. Water structure is not found to be strongly affected by the presence of DMSO. However, the percentage of water molecules which hydrogen bond to themselves is substantially reduced compared to pure water, with a large proportion of the hydrogens available for bonding associated with the lone pairs on the DMSO. These experimental findings are in good agreement with the assumptions made in the simple mean-field type model for hydrogen-bonded mixtures, developed by Luzar [J. Chem. Phys. 91, 3603 (1989)]. A general scheme for analyzing experimental data on the HH and OH pair correlation functions in terms of coordination numbers is presented. The hydrogen–hydrogen correlation in the solvent (water) is also used to discuss the interparticle correlations between solute (DMSO) particles.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 8460-8469 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The radial pair distribution functions gHH(r) and gOH(r) (to a good approximation) of 1 and 10 m solutions of lithium chloride in water have been obtained from neutron diffraction. It turns out that the intermolecular water structure in a solution of 10 m is affected considerably by the presence of ions—the number of hydrogen bonds is about 70% lower than in pure water. The intermolecular water structure in 1 m lithium chloride as well as the intramolecular water structure in both 1 and 10 m lithium chloride is not distinguishable from that of pure water in any measurable extent.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 6836-6847 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structure of liquid dimethylsulphoxide (DMSO) at 25 °C is explored using a combination of neutron diffraction with isotope substitution and computer simulation techniques. The potentials used in the computer simulation consist of Coulomb and 6-12 Lennard-Jones interactions for each of the carbon, oxygen, and sulfur sites on the molecule. To interpret the neutron diffraction data most effectively, it is necessary to refine both the molecular internal structure and the intermolecular contributions to the measured structure factors at the same time in order to separate the intermolecular terms correctly, because there is a large degree of overlap between intramolecular and intermolecular distances. This renders the data far more sensitive to the intermolecular forces than if this analysis were not performed. Direct comparison of neutron diffraction data and computer simulation results indicates that existing models of the molecular force field give a sensible description of the liquid structure, although there are some discrepancies which are not fully understood at this time. The question of whether this material can be regarded as an associated liquid, as it is frequently referred to, is discussed. All tests for association that have so far been applied to both the diffraction data and the computer simulation results do not indicate a highly ordered molecular association in the liquid.
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  • 5
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 8161-8168 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 14201-14204 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 1897-1903 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: New data on the structure of water in the aqueous system LiCl⋅RH2O, with R=4, are presented for the liquid, supercooled liquid, and glass states. The results are compared to an earlier study of the system LiCl⋅6H2O [J. Chem. Phys. 103, 1886 (1995)]. Many of the qualitative trends seen for R=6 are similar for R=4, but there is evidence that the water structure is even more severely disrupted than for R=6. In the liquid state the distribution functions appear to be dominated by the packing of hydrated ions, rather than by hydrogen bonding forces. The latter partly reassert themselves in the supercooled and glass states. H/D isotope substitution throws some light on the first structure diffraction peak (FSDP) at 0.5 A(ring)−1 which is correlated with the nonhydrogenated components. This peak is not therefore the signature of long range water concentration fluctuations, but must be due to some weak periodicity in the underlying longer range order. © 1995 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 4123-4132 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Neutron diffraction data on water, employing the technique of hydrogen/deuterium isotope substitution, are reported at three thermodynamic states above the boiling point. The structural information is analyzed in terms of the partial radial distribution functions, OO, OH, and HH, which are extracted from the neutron data. It is found that temperature affects mainly the medium and longer range order in the liquid, while density plays a significant role in controlling the degree of hydrogen bonding. To understand the structure of water obtained from these data it appears that many-body cooperative interactions have to be correctly accounted for.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 1886-1896 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using the technique of hydrogen and deuterium substitution, the structure of water in concentrated lithium chloride aqueous solutions (LiCl⋅6H2O) is explored for the liquid, supercooled liquid, and glass states. It is found that changes in structure between the glass and supercooled states are minor, but that a major change in water structure occurs as the supercooled liquid is heated above the temperature of peritexy of the penta-hydrate (Tp=207 K). In particular the 4.4 A(ring) peak in the OO pair correlation function of pure water, which is normally viewed as indicating tetrahedral short range coordination in water, is absent in the LiCl solution at the same temperature, but reappears strongly in the glass and supercooled states. Corresponding changes occur in the HH and OH correlation functions. In addition, correlations appear to extend nearly twice as far in the glass and supercooled liquid, compared to the room temperature liquid. © 1995 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 7868-7872 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Neutron diffraction isotopic substitution experiments on liquid n-decane (C10H22) and n-eicosane (C20H42) are described. The intermolecular H–H structure function hHH(Q) and the intermolecular H–H correlation function ginterHH(r) are obtained without recourse to models of the intramolecular structure. The structure of the ginterHH(r) found at 2.5, 5.0, and 7.0 A(ring) corresponds to different shells in the H–H pair correlation function. In addition, ginterHH(r)〈1 for a considerable range, due to the screening of intermolecular correlations by intramolecular correlations. This "correlation hole'' effect is accentuated by extrapolation of the structure functions to the expected infinite wavelength limit, and shows good agreement with values determined from small-angle neutron scattering (SANS) data. All of these features are in good agreement with the results of molecular dynamics simulations for the closely related system C13H28.
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