Near infrared spectra and the disrupted network model of normal and supercooled water

C. A. Angell, V. Rodgers

Research output: Contribution to journalArticle

101 Scopus citations

Abstract

The near IR (overtone) spectra of water, H2O-D2O solutions, and a glass-forming glycerol +D2O solution have been measured in the temperature range 80 to -30 °C (-120 °C for the glycerol +D2O solution) using emulsion samples to gain access to the deep supercooling range. At -30 °C the intensity attributed to weakly hydrogen bonded -OH is greatly diminished and a small extrapolation in the latter case leads to a spectrum closely similar to that of the vitreous glycerol +D 2O solution. This is a very broad spectrum, extending from 1.4-1.65 μm, which we associate with a fully bonded and immobile quasilattice in which there is a distribution of hydrogen bond strengths. The changes in intensity which occur with rise in temperature are seen to be consistent with an "exciting across the centroid" model (a weak bond⇄strong bond exchange) suggested by Stillinger and Rahman on the basis of MD calculations. The enthalpy change for this process is found to be 3.0 kcal/mol, consistent with light-scattering data for the hydrogen bond-breaking energy.

Original languageEnglish (US)
Pages (from-to)6245-6252
Number of pages8
JournalThe Journal of chemical physics
Volume80
Issue number12
StatePublished - Dec 1 1983
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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