Infrared spectra of water. II : Dynamics of H2O(D2O) molecules

Y. Maréchal

doi:doi:10.1051/jp2:1993151

Issue		J. Phys. II France Volume 3, Number 4, April 1993


Page(s)		557 - 571
DOI		https://doi.org/10.1051/jp2:1993151

DOI: 10.1051/jp2:1993151
J. Phys. II France 3 (1993) 557-571

Infrared spectra of water. II : Dynamics of H ₂O(D ₂O) molecules

Y. Maréchal

Département de Recherche Fondamentale sur la Matière Condensée, SESAM/PCM, Centre d'Etudes Nucléaire, 85X, F-38041 Grenoble Cedex, France

(Received 9 October 1992, accepted 22 December 1992)

Abstract
Spectra of $\varepsilon''$ (imaginary dielectric constant) of water in the IR region, obtained as described in a previous article by using attenuated total reflection (ATR) techniques, are analyzed. Criteria are presented which allow us to define, on the basis of spectroscopical arguments only, the low temperature spectrum $\varepsilon''$ ( $T_{\rm L}$ ) and the high temperature spectrum $\varepsilon''$ ( $T_{\rm H}$ ) on which any spectrum at temperature T, in the range $-5~^\circ {\rm C}$ to $80~^\circ {\rm C}$ , may be decomposed. These spectra display novel features : their $\nu_{\rm s}$ bands (intramolecular stretch) have shapes which have great similarities in both spectra ; the $\delta$ band (intramolecular bend) of the high temperature spectrum $\varepsilon''$ ( $T_{\rm H}$ ), has a simple shape with no apparent structure, which may be approximated, with a good precision, by a Lorentzian curve. A discussion of the origin of these features reveals a new picture of water at a molecular level : it is made of H ₂O molecules which either perform rotations of a vibrational character (librations) around their three axes and appear in $\varepsilon''$ ( $T_{\rm L}$ ) or perform rotations around their C ₂ symmetry axis z of a diffusional (relaxational) character. H ₂O molecules of the latter type appear in $\varepsilon''$ ( $T_{\rm H}$ ). Their concentration reaches $\approx 35~\%$ at 0 $^\circ {\rm C}$ (1 atm.) and $\approx 90~\%$ at $100~^\circ {\rm C}$ (1 atm.). They have rotational energies around z greater than the maximum of the potential energy governing this rotation. Around their other two axes they perform librations which qualitatively do not differ from those performed by molecules appearing in $\varepsilon''$ ( $T_{\rm L}$ ). The estimated correlation time, or average time during which phase coherence of $\delta$ vibrations in these molecules is kept, falls in the range 10^-14- 10^-13 s, as deduced from the Lorentzian shape of the $\delta$ band in $\varepsilon''$ ( $T_{\rm H}$ ). The analysis of these spectra also indicates that the " $\delta + \nu_{\rm L}$ " band borrows its intensity from $\nu_{\rm s}$ via a cubic term in the vibrational potential.