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Aqueous dimethyl sulfoxide solutions: Inter- and intra-molecular dynamics

J. Chem. Phys. 116, 4643 (2002); doi:10.1063/1.1449864

Issue Date: 15 March 2002

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Piotr P. Wiewiór, Hideaki Shirota, and Edward W. Castner, Jr.
Rutgers, The State University of New Jersey, Department of Chemistry and Chemical Biology, Piscataway, New Jersey 08854
The inter- and intra-molecular dynamics of aqueous dimethyl sulfoxide (DMSO) solutions have been measured using optical heterodyne-detected Raman-induced Kerr effect spectroscopy. Solutions were studied over the entire range of composition at 294 K. The Kerr transients characterize both the underdamped inter- and intra-molecular vibrational motions, as well as the overdamped, diffusive orientational motions. The longer diffusive relaxation time constant tau2 is assigned to DMSO reorientation, and varies strongly with mole fraction of DMSO. The shorter time constant tau1 is assigned to water reorientation, and the value of 1.0 ps is nearly invariant across the range of solution composition. The solutions deviate substantially from hydrodynamic scaling behavior, since the ratio of DMSO reorientation time constant normalized by shear viscosity tau2/eta is not a linear function of mole fraction. The peak frequencies for three of five low frequency intramolecular vibrations decrease with increasing water content. Both anisotropic and isotropic Kerr transients are recorded. The isotropic Kerr transient is dominated by the partially depolarized nu10 symmetric C–S–C stretching vibration at 670 cm–1. Electronic structure calculations for isolated DMSO, perdeuterated DMSO (d6-DMSO), and water are carried out using semi-empirical (PM3), density functional (B3LYP), and MP2 methods. Basis sets up to 6-311 + + G(d,p) are used and vibrational frequencies are calculated within the harmonic approximation. An unusual hemispherical shape is obtained for the electrostatic potential (ESP) about the DMSO oxygen. This hemispherical ESP was consistently observed for all levels of electronic structure theory and all basis sets that were used. Calculated polarizabilities permit us to estimate the anisotropic Kerr signal for an isolated DMSO molecule to be 79 times greater than for an isolated water molecule. ©2002 American Institute of Physics.
History: Received 17 October 2001; accepted 17 December 2001
Permalink: http://link.aip.org/link/?JCPSA6/116/4643/1
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KEYWORDS and PACS

Keywords
PACS
  • 34.20.Gj
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Intermolecular and atom–molecule potentials and forces
  • 34.30.+h
    Atomic and molecular collision processes and interactions Intramolecular energy transfer; intramolecular dynamics; dynamics of van der Waals molecules
  • 42.65.Jx
    Optics Nonlinear optics Beam trapping, self-focusing, and thermal blooming
  • 66.20.+d
    Transport properties of condensed matter (nonelectronic) Viscosity of liquids; diffusive momentum transport
  • YEAR: 2002

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0021-9606 (print)   1089-7690 (online)
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