Raman Spectral Studies of the Effects of Temperature on Water Structure (1967)

Integrated Raman intensities of the spectral contour arising from the intermolecular librational motions of pure water have been obtained in the temperature range of ∼10°—95°C. In addition, integrated intensities of nearly symmetric librational components centered near ∼475 and ∼710 cm−1 were obtained from manual contour analysis according to two components. However, contour analysis was also accomplished by means of a special-purpose analog computer, and three Gaussian librational components having average frequencies of 439, 538, and 717 cm−1 were thus revealed. The total contour intensity, the manually determined component intensities, and the Gaussian component intensities were found to have the same temperature dependence, and that dependence was found to be in excellent quantitative agreement with the previously reported temperature dependence of the hydrogen-bond-stretching intensity [J. Chem. Phys. 44, 1546 (1966)]. Integrated Raman intensities of pure water were also obtained in the temperature range of 10°—90°C for the intramolecular valence and deformation contours in the spectral region of ∼2800–3900 cm−1, and near 1645 cm−1, respectively. The integrated intensity of the deformation contour was found to be nearly independent of temperature, but the total integrated intensity of the intramolecular valence contour was found to decrease with increasing temperature. However, heights of the high-frequency portion of the intramolecular valence contour were observed to increase, whereas heights of the low-frequency portion were observed to decrease at nearly the same rate, with increasing temperature. An isosbestic point was also found at approximately 3460 cm−1. Further, computer analysis revealed the existence of four Gaussian components having opposite temperature dependences in pairs—two intense valence components at ∼3247 and ∼3435 cm−1 were found to decrease in intensity with increasing temperature, and two weak components at ∼3535 and ∼3622 cm−1 were found to increase in intensity. Computer analysis of infrared absorbance spectra also revealed four Gaussian components at approximately 3240, 3435, 3540, and 3620 cm−1. The quantitative agreements involving temperature dependences of the intermolecular hydrogen-bond-stretching and librational intensities, as well as the intramolecular valence data, would appear to preclude models of water structure involving consecutive hydrogen-bond breakage. Continuum models of water structure are also precluded by the inter- and intramolecular intensity dependences, and particularly by the isosbestic point in the intramolecular valence region, but a model involving an equilibrium between two forms of water is consistent with all of the data. The two forms refer to water molecules which have or have not surmounted a barrier arising from a partially covalent hydrogen-bond potential of C2v symmetry, and they may be described as nonhydrogen-bonded monomeric water, and as lattice water, respectively. Polarized argon-ion-laser—Raman spectra were also obtained in the intermolecular frequency region of the water spectrum, and the depolarization ratios of the intermolecular Raman bands were found to be in complete agreement with predictions from intermolecular C2v symmetry. Studies of the intramolecular valence region were also made with polarized mercury excitation, and the spectra were analyzed by the analog method. Short-lived CS intramolecular perturbations were indicated by the observed depolarization ratios of the four Gaussian valence components. Accordingly, CS intramolecular valence perturbations occur in the lattice water, as well as in the nonhydrogen-bonded water, but the perturbations are of little importance on the intermolecular time scale.