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Revisiting the Aqueous Solutions of Dimethyl Sulfoxide by Spectroscopy in the Mid- and Near-Infrared: Experiments and Car–Parrinello Simulations
Version 2 2015-12-17, 10:43
Version 1 2015-11-19, 05:43
journal contribution
posted on 2015-12-17, 10:43 authored by Victoria
M. Wallace, Nilesh R. Dhumal, Florian M. Zehentbauer, Hyung J. Kim, Johannes KieferThe
infrared and near-infrared spectra of the aqueous solutions
of dimethyl sulfoxide are revisited. Experimental and computational
vibrational spectra are analyzed and compared. The latter are determined
as the Fourier transformation of the velocity autocorrelation function
of data obtained from Car–Parrinello molecular dynamics simulations.
The experimental absorption spectra are deconvolved, and the excess
spectra are determined. The two-dimensional excess contour plot provides
a means of visualizing and identifying spectral regions and concentration
ranges exhibiting nonideal behavior. In the binary mixtures, the analysis
of the SO stretching band provides a semiquantitative picture of the
formation and dissociation of hydrogen-bonded DMSO–water complexes.
A maximum concentration of these clusters is found in the equimolar
mixture. At high DMSO concentration, the formation of rather stable
3DMSO:1water complexes is suggested. The formation of 1DMSO:2water
clusters, in which the water oxygen atoms interact with the sulfoxide
methyl groups, is proposed as a possible reason for the marked depression
of the freezing temperature at the eutectic point.
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DMSO concentrationDimethyl Sulfoxidevelocity autocorrelation functionnonideal behaviorsulfoxide methyl groupsAqueous Solutionsabsorption spectraequimolar mixturecontour plotclusterFourier transformationcomplexvibrational spectradimethyl sulfoxideeutectic pointconcentration rangesdynamics simulationswater oxygen atoms
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