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Incomplete mixing versus clathrate-like structures: A molecular view on hydrophobicity in methanol–water mixtures

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Abstract

The underlying molecular mechanisms of macroscopic excess properties were studied by molecular dynamics simulations for different compositions of methanol–water mixtures. Structural data (nearest neighbor relationships, clustering analysis) and dynamic data (hydrogen bond lifetimes, rotational autocorrelation, translational diffusion) were evaluated. Nearest neighbor relationships provide quantitative evidence and a pictorial description of incomplete mixing at the molecular level as a source for mixture anomalies, while a comparative study of water surrounding methyl moieties versus water in the bulk-like environment provides evidence against the hydrophobicity model of clathrate-like hydration. Furthermore, the formation or breakdown of the system-wide hydrogen bonding network at a critical threshold of approximately equimolar mixture is perceived to separate the mixture system into two hydrogen bonding regimes: hydrogen-bonded water clusters embedded in methanol for mixtures with low water content and methanol molecules within a system-wide hydrogen-bonded water network for mixtures with high water content.

Structural and dynamic properties of methanol-water mixtures were studied by molecular dynamics simulations to identify the molecular mechanisms of hydrophobicity. Nearest neighbor relationships provide quantitative evidence of incomplete mixing as a source for mixture anomalies.

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Acknowledgments

We thank Joachim Groß (University of Stuttgart) for helpful discussions. This work was funded by SimTech Cluster of Excellence at the University of Stuttgart.

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  1. Institute of Technical Biochemistry, University of Stuttgart, Allmandring 31, 70569, Stuttgart, Germany

    Sven P. Benson & Jürgen Pleiss

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Correspondence to Jürgen Pleiss.

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Benson, S.P., Pleiss, J. Incomplete mixing versus clathrate-like structures: A molecular view on hydrophobicity in methanol–water mixtures. J Mol Model 19, 3427–3436 (2013). https://doi.org/10.1007/s00894-013-1857-1

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