Cooperative interactions in the hydration of dimethyl ether (DME) relative to its purely hydrophobic analog, propane, are analyzed by expressing the free energy of hydration in terms of an “inner-shell” contribution from water molecular packing and chemical association, and an “outer-shell” contribution described by the mean binding energy of the solute to the solution and fluctuations in this binding energy. We find that nonadditive, cooperative interactions associated with strong correlations in the binding energy fluctuations of the methyl groups and ether oxygen play a dominant role in the hydration of DME relative to propane. The electrostatic nature of these interactions is revealed in a multi-Gaussian analysis of hydration substates, which shows that the formation of favorable ether oxygen-water hydrogen bonds is correlated with less favorable methyl group-water interactions, and vice versa. We conclude that the group additive distinction between the hydrophobic hydration of the DME methyl groups and hydrophilic hydration of the ether oxygen is lost in the context of these cooperative interactions. Our results also suggest that the binding energy fluctuations of constituent hydrophobic/hydrophilic groups are more sensitive than local water density fluctuations for characterizing the hydration of heterogeneous interfaces.
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21 April 2010
Research Article|
April 16 2010
Cooperative hydrophobic/hydrophilic interactions in the hydration of dimethyl ether
S. Utiramerur;
S. Utiramerur
William G. Lowrie Department of Chemical and Biomolecular Engineering,
Ohio State University
, Columbus, Ohio 43210, USA
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M. E. Paulaitis
M. E. Paulaitis
a)
William G. Lowrie Department of Chemical and Biomolecular Engineering,
Ohio State University
, Columbus, Ohio 43210, USA
Search for other works by this author on:
S. Utiramerur
M. E. Paulaitis
a)
William G. Lowrie Department of Chemical and Biomolecular Engineering,
Ohio State University
, Columbus, Ohio 43210, USA
a)
Electronic mail: [email protected].
J. Chem. Phys. 132, 155102 (2010)
Article history
Received:
December 23 2009
Accepted:
February 10 2010
Citation
S. Utiramerur, M. E. Paulaitis; Cooperative hydrophobic/hydrophilic interactions in the hydration of dimethyl ether. J. Chem. Phys. 21 April 2010; 132 (15): 155102. https://doi.org/10.1063/1.3367977
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