INFRARED-SPECTRA OF WATER .1. EFFECT OF TEMPERATURE AND OF H/D ISOTOPIC DILUTION

The implementation of a cell operating with the technique of Attenuated Total Reflection (ATR) enabled us to obtain good quality IR spectra of water for the whole region above 750 cm-1 (which is the limit of the effect of the cutoff wave number of the crystal) and up to 5000 cm-1. ATR spectra have been recorded as a function of temperature ranging from -5-degrees-C to 80-degrees-C and of H/D molar concentration c(0 < c < 1). They have been transformed into spectra in epsilon", using the Bertie-Eysel iteration procedure. In this paper evolutions of these spectra in epsilon" upon variations of these two parameters c and T are investigated and analyzed. It is shown that any experimental spectrum in epsilon" of a mixture of normal and heavy water is a superposition of three spectra due to pure H2O, pure D2O, and a spectrum that is only slightly dependent upon isotopic concentration c and is consequently mainly due to HDO. Analysis of this slight dependence upon c allows precise conclusions concerning vibrational interactions for both bending bands delta and stretching bands nu-s to be reached. Evolution of spectra with temperature unambiguously shows that all spectra at temperature T may be decomposed into a low temperature spectrum and a high temperature spectrum. The coefficient defining this decomposition [Eqs. (11) and (14)] displays a quadratic variation with T. It is the same for H2O, D2O, and HDO within the precision of the experiment. A low temperature spectrum corresponding to a (slightly distorted) H-bond network with no other defects, as well as a high temperature spectrum due to "defects" cannot, however, be determined without any further assumption. Limits for values of the concentration of defects alpha(T) may nevertheless be established.