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• W2069496559 abstract "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 °C to 80 °C and of H/D molar concentration c(0&lt;c&lt;1). They have been transformed into spectra in ε″, using the Bertie–Eysel iteration procedure. In this paper evolutions of these spectra in ε″ upon variations of these two parameters c and T are investigated and analyzed. It is shown that any experimental spectrum in ε″ 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 δ and stretching bands νs 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 α(T) may nevertheless be established." @default.
• W2069496559 created "2016-06-24" @default.
• W2069496559 creator A5037027768 @default.
• W2069496559 date "1991-10-15" @default.
• W2069496559 modified "2023-10-14" @default.
• W2069496559 title "Infrared spectra of water. I. Effect of temperature and of <i>H</i>/<i>D</i> isotopic dilution" @default.
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• W2069496559 doi "https://doi.org/10.1063/1.461630" @default.
• W2069496559 hasPublicationYear "1991" @default.
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