The transmission spectra in the intramolecular stretching region have been measured for thin films of H2O and D2O polycrystalline ice Ih and amorphous solid water. The data have been reduced to obtain the complex refractive index in this region via an iterative procedure designed to account for reflection and interference losses. Details of this procedure are described. The values which result from this analysis are converted to give the imaginary part of the dielectric permittivity as a function of wavelength for each sample. In this form the spectra are examined and compared to one another, with regard to recent experimental and theoretical studies. We conclude that it is difficult to obtain detailed structural information for the amorphous solid from an analysis of the OH (OD) stretching vibrational spectrum alone.

The vibrational spectroscopy of ice Ih, amorphous solid water, and liquid water are discussed from a unified point of view. In particular, the various forms of interplay between positional and orientational order/disorder, intermolecular coupling, changes in intramolecular properties induced by hydrogen bonding, Fermi resonance, and the like are shown to account for the observed spectra of these condensed phases of water. The random network model of amorphous solid and liquid water are also discussed.

We report the results of an analysis of the OH stretching region of the vibrational spectrum of ice Ih. The model of ice Ih discussed in an earlier paper [J. Chem. Phys. 69, 3483 (1978)] is considerably improved in that a larger section of the proton disordered lattice is included in the dynamical description, the shift in the OH stretching force constant on hydrogen bonding is calculated from molecular properties, the interaction force constants are re-evaluated using newer and more extensive data, and Fermi resonance and internal field effects on the lattice dynamics are accounted for. We show the following: (i) Strong coupling between OH oscillators on different molecules is responsible for the major features of the vibrational spectrum, namely, its breadth and gross distribution of intensity. (ii) Internal field effects, which lead to wave vector dependent polar mode mixing in a proton ordered model of ice I, do not influence the distribution of intensity in the Raman spectrum of proton disordered ice Ih, despite the fact that the internal field does play an important role in altering the states of the system. Our calculations provide no support for the suggestion that structure in the Raman spectrum of ice Ih can be assigned using the Lyddane–Sachs–Teller relation, i.e., that structure in the Raman spectrum can be related to system modes arising under the influence of the longitudinal field. (iii) Fermi resonance between the OH stretching mode and the overtone of the bending mode has more influence on the vibrational spectrum of D2O ice Ih than on that of H2O ice Ih. The inclusion of Fermi resonance in the description of the OD stretching dynamics materially improves the agreement between the predicted and observed vibrational spectra. However, the redistribution of spectral intensity attributable to Fermi resonance is a second order effect relative to the distribution of intensity determined by the interaction between OH oscillators on different molecules. (iv) The change in OH stretching frequency when a water molecule is incorporated in ice Ih can be accounted for self-consistently using only the known free molecule anharmonic potential energy coefficients and a parametric description of the dependence of the harmonic force constants on the strength of hydrogen bonding. This finding validates and provides an interpretation of the quasiharmonic representation of OH stretching motions used in our earlier work.

We describe a theoretical interpretation of the OH stretching region of the vibrational spectrum of ice Ih derived from a study of extended models. The principle conclusions are the following: (i) The breadth and distribution of vibrational modes, and of intensity in the Raman and infrared spectra, are dominated by the influence of strong intermolecular coupling. The intermolecular coupling is comparable in strength to the intramolecular coupling. Long range couplings between molecules not directly hydrogen bonded mainly serve to make the features of the spectrum more diffuse than they would otherwise be, but have no great influence on the spectral distribution. (ii) The intramolecular OH stretch-OH stretch coupling in ice Ih is of opposite sign to that in the gas phase. (iii) The vibrational modes of ice Ih are found to be complex mixtures of molecular motions, so identification of regions of the Raman or infrared spectra with particular isolated molecule modes is not useful. Rather good agreement is obtained between the Raman and infrared spectra predicted and those observed. Some deficiencies of the model, associated with residual discrepancies between theory and experiment, are discussed.

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