The Raman scattering by the stretching modes of H2O and D2O in the ordered phases ice II and ice IX is reported for temperatures between 100 and 25 °K. The observed features are assigned to k=0 modes with the aid of polarization data from oriented crystals of D2O ice II and the normal coordinate calculations which have previously explained the infrared spectra [J. E. Bertie and F. E. Bates, J. Chem. Phys. 67, 1511 (1977)]. It is shown that normal coordinate, bond moment, and bond polarizability, calculations satisfactorily explain the frequencies and relative intensities in both the infrared and Raman bands due to the D2O stretching modes in these phases. These Raman bands are nearly insensitive to the order or disorder of the water molecules in phases of ice. The O–D stretching modes of ice IX that have large infrared intensities have weak Raman intensities, and no longitudinal optic modes can be clearly identified in the Raman spectra. The frequencies of the LO modes have been estimated for ices II and IX. The magnitudes of the LO–TO splittings suggest that the infrared transmission spectra may be broadened by reflection effects resulting from the dispersion of the refractive index, and the sharpness of the Raman bands suggests that the breadth of the infrared bands is not primarily due to Fermi resonance with high-order overtone and combination levels, as was previously proposed.

The Raman scattering by the translational and rotational vibrations of normal and deuterated ice II and ice IX at atmospheric pressure and 35–100 K is reported. The infrared absorption by deuterated ice II and ice IX at atmospheric pressure and 4.3 K is also reported. Imperfect, but useful, polarized Raman spectra of single crystals of ice II have indicated the symmetries of the vibrations. The translational vibrations have been reproduced remarkably well by normal coordinate and intensity calculations based on very simple force fields and models of the dipole moment and polarizability changes. No features could be assigned to longitudinal optic modes. Attempts to calculate the rotational and translational vibrations from the one force field were made for five force fields. No force field reproduced the observed separation of translational and rotational displacements in the normal vibrations for the actual structure. This experimental fact, that the vibrations are translational or rotational but not mixed, will provide a severe test for potential functions for the interaction between water molecules. A correction is given to the sample temperature cited in a previous publication about the OH and OD stretching vibrations of these ices [J. E. Bertie and B. F. Francis, J. Chem. Phys. 72, 2213 (1980)].

Several different measurements 1,2,3,4 of the integral intensities in the Raman spectra of polycrystalline ice are discussed. The polarization derivatives derived from the intensity measurements are compared. (AIP)

The far-infrared absorption spectrum of the tetragonal adamantane II contains the expected three bands, but with an unusual disparity between their intensities. Their frequencies agree well with those calculated by Luty, and coincide with three of the features in the published Raman spectrum which, however, contains at least 12 features instead of the expected five.

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