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  • 1
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Several porous silicon, siloxene (Si6H6O3), heat-treated siloxene, and layered polysilane (Si6H6) samples have been studied with K- and L-edge x-ray photoabsorption, photoemission, and powder x-ray diffraction. The x-ray absorption of layered polysilane and porous-Si are found to be remarkably similar. In particular, the K absorption edges of these samples shift by about 0.4–0.6 eV to higher energy relative to crystalline silicon. Siloxene samples heated to 400 °C in inert gas are best described as a mixture of SiO2 and amorphous-Si. When heat-treated siloxene is studied by photoelectron spectroscopy (surface sensitive) it resembles SiO2, when it is studied by x-ray absorption (bulk and surface) features from both SiO2 and amorphous-Si are observed and when it is studied by x-ray diffraction (bulk measurement) it resembles amorphous-Si. The SiO2 is therefore predominantly at the surface and heat-treated siloxene is very small amorphous-Si particles coated with SiO2. The Si L edge of heat-treated siloxene is not shifted significantly with respect to crystalline Si, unlike that of porous-Si, as-prepared siloxene, or layered polysilane. Taken together, these results suggest that heat-treated siloxene does not resemble electrochemically prepared porous-Si but that it might resemble rapid thermal annealed porous-Si. On the other hand, we believe that layered polysilane and unheated porous-Si may be related.
    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 110 (1999), S. 6475-6483 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Tetrahydrofuran, a water-soluble cyclic ether molecule, is well known for its ability to form clathrate hydrates (cubic structure II, melting point 277.5 K). An aqueous solution of THF (17:1 molecular ratio) was hyperquenched (cooled at a rate of 106 Ks−1) to 77 K to give recoverable samples of ∼1 g of metastable amorphous material. The crystallization process was studied on three complementary length scales by x-ray powder diffraction, quadrupole echo double resonance (QEDOR) NMR spectroscopy, and Raman spectroscopy as the amorphous material was annealed at temperatures between 80 and 190 K. Results show that phase separation of the two components occurred predominantly during the annealing process, resulting in clusters of crystalline THF and ice Ic before clathrate hydrate crystallization was initiated. During the hyperquenching process, the decreasing molecular mobility of water molecules between room temperature and the fictive temperature (the temperature below which the solution becomes structurally immobilized upon hyperquenching) inhibits growth of the crystal nuclei that normally would result in crystalline clathrate hydrate formation. Annealing the samples between 110–140 K showed that the local hydrogen bonded O–H--O structure of the water molecules changed toward the arrangement characteristic of crystalline ice Ic. We propose that this process forces the THF out of the glassy solution, thus increasing the THF cluster size in the deposit so that these become visible to diffraction. Further annealing, above 150–160 K caused large-scale growth of crystalline clathrate hydrate material, which then could be associated with a reduction in the THF cluster size, and ice Ic. © 1999 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 8478-8484 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In order to investigate subtle differences in the local structure and bonding of amorphous ices, glassy liquid water was produced by rapid cooling of micrometer sized water droplets. Samples were first studied with power x-ray diffraction (PXRD) and differential scanning calorimetry (DSC) to ensure that the production technique resulted in amorphous material with low crystalline content. Solutions containing 5% D2O in H2O and 5% H2O in D2O were vitrified, cooled to 12 K, and used to collect Raman spectra of the decoupled O–D (ΔνOD=2440 cm−1) and O–H (ΔνOH=3302 cm−1) vibrations, respectively. Samples were then annealed from 90 to 180 K in temperature intervals of 10 K. During each annealing step the samples were held isothermally for 15 min before rapidly cooling them back down to 12 K for data collection. The transition from amorphous to crystalline material was observed to occur between 150 and 160 K. Raman frequency shift data were then used to estimate the distribution in the hydrogen-bonded O–H––O distances using known correlations. The local bond strengths and O–H––O distances in vitrified liquid water were found to be very similar to those in vapor-deposited amorphous water. © 1998 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 7009-7010 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The difference in energy between ice Ic and Ih has been determined calorimetrically in order to help test water–water potential energies. It is −50.5±2.2 J mol−1 at 200 K, and −47±∼3 J mol−1 when adjusted to zero temperature using measured vibrational frequencies.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 2708-2711 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The far-infrared spectrum of ice VIII as recovered at ∼100 K and zero pressure has translational and rotational bands at 162 and 455 cm−1, respectively. They are undoubtedly due to the Eu translational vibration in the x, y plane and the Eu rotational vibration about the x, y axes. The correlation of the vibrations of ice VIII with the zone-center and -boundary vibrations of the centrosymmetric phase ice X is summarized.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 7244-7245 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The relative intensity of the in-phase and out-of-phase vibrations of intermolecularly coupled O–D--O–D pairs in ice Ic shows that the dipole-moment derivatives for the O–D stretching vibrations in ice Ic are within about 3° of the tetrahedral lines between water molecules. In the gas phase the dipole-moment derivatives are directed 25° outside the O–D bonds.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 5323-5328 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Raman spectrum of the uncoupled O–H and O–D stretching vibrations of HDO dissolved in H2O high-density amorphous ice, that was made from ice Ih, has been measured at 12 K for the sample as recovered at 77 K and after heating it at 5 K min−1 from 12 K to, successively, 80, 90, 100, ..., 170 K and annealing there for 5 min. The distribution of hydrogen-bonded O–H--O and O–D--O distances was estimated by using an experimental curve of the O–H stretching frequency as a function of the O--O distance in ice VII, as suitably adjusted using the frequency in ice I. The most probable bond length, as estimated from the peak frequency, is 2.83 A(ring), which is 0.08 A(ring) longer than the length in ice I, and the distribution of bond lengths has a width at half-height of 0.19 A(ring). When the sample was heated to 80, 90, 100, 110, and 120 K in succession, the peak frequency and the width at half-height, as measured at 12 K, decreased by amounts that corresponded to a decrease of the most probable distance from 2.83 to 2.76 A(ring) and a decrease of the width at half-height from 0.19 to 0.09 A(ring). The phase produced at 120 K is a low-density amorph, and it changes little after heating to 130 and 140 K. After heating to 150 K it changes to ice Ic, whose peak frequency implies an O--O distance of 2.75 A(ring).
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 6212-6212 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 4807-4809 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The integrated infrared intensity of the symmetric O–H stretching vibration of the water molecule increases by a factor of 220 when the vapor is condensed to ice I. The increase occurs for three reasons, the first of which is that the dipole moment of an isolated water molecule in its equilibrium configuration is near its maximum as a function of O–H distance. Its change with the symmetric stretch of the O–H bonds is, therefore, small, and so is the integrated absorptivity. The second is that when the molecule is put into the crystal, the dipole moment must, by symmetry, go to zero when the O–H distance is half the O--O distance, and this causes the dipole-moment derivative to become large and negative. The third is that each molecule is further polarized by the electric fields of neighboring molecules, and so its dipole moment is increased even further, which increases the magnitude of the dipole-moment derivative and hence of the integrated intensity.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 78-80 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ratio of the integrated absorption intensities of the ν3 and ν1 vibrations of H2O vapor is 20.6 [J. M. Flaud and C. Camy-Peyret, J. Mol. Spectrosc. 55, 278 (1975)] and so the dipole-moment derivatives for the stretching of the two bonds independently are 25.2° outside the bonds themselves. The corresponding ratio for the uncoupled D2O molecule isolated in H2O low-density ice I at∼100 K and zero pressure has been measured as 1.77 and 1.73, and for D2O isolated in the low-density H2O amorph as 1.90, 2.72, and 1.94 from the spectra of Devlin and his colleagues. The derivatives of the water molecule in ice are, therefore, directed along the bonds within the experimental uncertainty. The ratio of the integrated intensities of the ν3 and ν1 vibrations of H2O ice VIII at −10 °C and 32 kbar is 1.95 [D. D. Klug and Edward Whalley (in preparation)], which implies that the dipole-moment derivative is directed ∼2° outside the bond. This spectacular change of direction of the dipole-moment derivative on condensation is a newly recognized effect of hydrogen bonding.
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