|Author||Bertie, J. E. ♦ Whalley, E.|
|Source||United States Department of Energy Office of Scientific and Technical Information|
|Publisher||American Institute of Physics (AIP)|
|Subject Keyword||INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ♦ ABSORPTION ♦ ATOMS ♦ CONFIGURATION ♦ COOLING ♦ CRYSTALS ♦ DIAGRAMS ♦ ENERGY LEVELS ♦ FREQUENCY ♦ HEAVY WATER ♦ HYDROGEN ♦ ICE ♦ INFRARED RADIATION ♦ ISOMERS ♦ ISOTOPE EFFECTS ♦ LATTICES ♦ LOW TEMPERATURE ♦ MEASURED VALUES ♦ MIXING ♦ MOLECULES ♦ NUMERICALS ♦ ORGANIC FLUORINE COMPOUNDS ♦ OSCILLATIONS ♦ PENTANE ♦ PHASE DIAGRAMS ♦ PHOTOMETRY ♦ PREPARATION ♦ PRESSURE ♦ PROPANE ♦ QUANTITY RATIO ♦ ROTATION ♦ SAMPLING ♦ SPECTRA ♦ SPECTRAL SHIFT ♦ SPECTROSCOPY ♦ TABLES ♦ USES ♦ VAPORS ♦ VESSELS ♦ WATER|
|Abstract||The infrared spectra of Ices II, III, and V between 4000 and 350 cm<sup>-1</sup> were obtained. The ices were made at appropriate pressure and temperatures, cooled under pressure to liquid-nitrogen temperature, and removed from the pressure vessel. Mulls were made near liquid-nitrogen temperature using isopentane or perfluoropropane as mulling agents, and the spectra of the mulls at approximates 100 deg K were recorded. The spectra of ices made from H<sub>2</sub>O, D<sub>2</sub>O, 5% H<sub>2</sub>O in D<sub>2</sub>O, 5% D<sub>2</sub>O in H<sub>2</sub>O, and, for Ices II and III, 1% D<sub>2</sub>O in H<sub>2</sub>O were obtained. In general features, the spectra of pure H<sub>2</sub>O and D<sub>2</sub>O Ices II, III, and V are similar to those of Ice I. For most bands there is a shift of frequency from that in Ice I towards the vapor frequencies, but the shift is small compared with the shift between Ice I and the vapor. Ices II, III, and V are therefore essentially fully hydrogen bonded and are probably four coordinated. This agrees with a proposed structure for Ice III. In Ices II and III the bands due to the O-- H and the O--D stretching vibrations of HDO in dilute solution in D<sub>2</sub>O and H<sub>2</sub>O, respectively, show a good deal of fine structure, and are quite narrow, the half- width of the O--D bands being about 5 cm<sup>-1</sup>. These are by far the sharpest O- H (or O-- D) stretching vibrations of hydrogenbonded O-- H-----O groups so far observed. Clearly, breadth is not inherent in the O-- H stretching bands of O-- H------O. There is also a good deal of fine structure in the bands due to rotational vibrations of water molecules in Ices II and III, and much of this fine structure broadens and weakens when a small amount of H<sub>2</sub>O is added to D<sub>2</sub>O, and of D<sub>2</sub>O to H<sub>2</sub>O The only simple explanation of this, and of the fine structure of the O-- H stretching bands, is that the hydrogen atoms in Ices II and III are ordered. No corresponding fine structure occurs in Ice V, and the hydrogen atoms are probably disordered, as in Ice I.|
|Learning Resource Type||Article|
|Publisher Department||National Research Council, Ottawa|
|Journal||Journal of Chemical Physics|
|Organization||National Research Council, Ottawa|
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