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

Charles Angell, V. Rodgers

Research output: Contribution to journalArticle

101 Citations (Scopus)

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 - 1983
Externally publishedYes

Fingerprint

infrared spectra
glycerols
Glycerol
Infrared radiation
Water
water
Hydrogen bonds
hydrogen bonds
Supercooling
supercooling
Emulsions
Extrapolation
Light scattering
centroids
emulsions
extrapolation
Hydrogen
Enthalpy
light scattering
enthalpy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Near infrared spectra and the disrupted network model of normal and supercooled water. / Angell, Charles; Rodgers, V.

In: The Journal of Chemical Physics, Vol. 80, No. 12, 1983, p. 6245-6252.

Research output: Contribution to journalArticle

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