RAMAN INTENSITIES OF SINGLE CRYSTAL ICE $I_{h}$

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1977

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Ohio State University

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Raman intensities of single crystal $H_{2}O$, $D_{2}O$, and H0D ice $I_{h}$ were measured from ${-4}^\circ$ C to ${-150}^\circ C$. The cc, aa, ca, and aa (c is the unique axis) polarizability components were measured from 20 $cm^{-1}$ to 4000 $cm^{-1}$. Shoulders were observed on the high frequency side of the $\nu_ {OH}$ and $\nu_{OD}$ bands of HOD which we attribute to combination bands between $\nu_{OH}$ and $\nu_{OD}$ and lattice modes. The intensities for the OH stretching region were interpreted using bond polarizability theory. The ratio of anisotropy to mean polarizability for the OH bond was found to be 1.81. From an analysis of the intensities, we conclude that the hydrogen atoms that lie on the c axis have more linear hydrogen-bonding than those that are equatorial to the c axis. Although the effect of intermolecular coupling of OH stretching vibrations is evident in the spectra, it is not primarily responsible for the breadth of the isotropic part of the symmetric OH stretch band at ${-4}^\circ C$. Evidence is presented for coupling of librational modes. Comparisons are made between the spectra of ice at ${-4}^\circ C$, liquid water, and amorphous ice.

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Author Institution: Western Regional Research Laboratory, Agricultural Research Service, USDA; Midland Macromolecular Institute, Agricultural Research Service, USDA

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