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Spectroscopy and dynamics of mixtures of water with acetone, acetonitrile, and methanol

J. Chem. Phys. 113, 11222 (2000); doi:10.1063/1.1328072

Issue Date: 22 December 2000

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Dean S. Venables and Charles A. Schmuttenmaer
Department of Chemistry, Yale University, 225 Prospect Street, P.O. Box 208107, New Haven, Connecticut 06520-8107
Binary mixtures of water with acetone, acetonitrile, and methanol over their entire range of compositions have been studied spectroscopically and by using molecular dynamics (MD) simulations. We report absorption coefficients and indices of refraction over a frequency range from 3 to 55 cm–1, and from 400 to 1200 cm–1. The far-infrared absorption of the mixtures is substantially less than that for ideal mixtures, and Debye time constants calculated from the spectra are longer for the real than for the ideal mixtures. Significant composition dependence is observed in the high frequency librational spectra of the mixtures, and is reproduced by the MD simulations. Single dipole and angular velocity spectra are also reported, as are detailed changes in the hydrogen bonding environment in the mixtures. There is a loss of tetrahedral water structure on mixing, yet water molecules have a strong tendency to aggregate, especially in the acetone and acetonitrile mixtures. Spatial distribution functions are reported for the acetone/water system. ©2000 American Institute of Physics.
History: Received 25 July 2000; accepted 2 October 2000
Permalink: http://link.aip.org/link/?JCPSA6/113/11222/1
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Supplemental Material

KEYWORDS and PACS

Keywords
PACS
  • 78.30.Cp
    Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Infrared and Raman spectra Liquids
  • 33.20.Ea
    Molecular properties and interactions with photons Molecular spectra Infrared spectra
  • 61.20.Ja
    Structure of solids and liquids; crystallography Structure of liquids Computer simulation of liquid structure
  • 78.20.Ci
    Optical properties, condensed-matter spectroscopy and other interactions of radiation and particles with condensed matter Optical properties of bulk materials and thin films Optical constants (including refractive index, complex dielectric constant, absorption, reflection and transmission coefficients, emissivity)
  • YEAR: 2000

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (61)
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