Hydration Structure and Interfacial Properties of Water near a Hydrophobic Solute from a Fundamental Measure Density Functional Theory

Bymaster, Adam; Dominik, and Aleksandra; Chapman, Walter G.

doi:10.1021/jp073762q

Cited by 18 publications

(24 citation statements)

References 76 publications

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“…Here, we extend this model to describe fluids of spherical associative monomers of diameter σ, and more specifically water, that is modeled within the SAFT-VR formalism by one sphere and four associative sites in a tetrahedral geometry 43 , a model originally proposed by Bol 42 that has become very popular and has found many successful applications 31,35,[43][44][45][46][47][48] . Thus, we have followed our previous work 40 11 .…”

Section: Introductionmentioning

confidence: 99%

Nonlocal Density Functional Theory and Grand Canonical Monte Carlo Molecular Simulations of Water Adsorption in Confined Media

et al. 2014

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We present in this paper a study of water adsorption behavior in confined media by using on the one hand a Non-Local Density Functional Theory (NLDFT) coupled with the SAFT-VR equation of state and, on the other hand, Grand Canonical Monte-Carlo (GCMC) molecular simulations. The present work is a second step in an ongoing NLDFT/SAFT-VR coupling. The first step has focused on the monomer contribution and especially in the way to extend the dispersive terms of the monomer contribution of SAFT-VR in the NLDFT formalism. In the present work, the theory has been extended by introducing the associative contribution due to hydrogen bonding and is applied to water, which is modeled as one sphere with four identical associating sites placed in a tetrahedral geometry with the same interaction parameters for both theory and simulations. NLDFT/SAFT-VR and GCMC results for density distributions of water in graphitic slit-like micropores and mesopores are shown to be in good agreement. Moreover, the capillary condensation and evaporation were investigated with the theoretical model in micro and mesopores, and also in the case of activated surfaces.

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Section: Introductionmentioning

confidence: 99%

Nonlocal Density Functional Theory and Grand Canonical Monte Carlo Molecular Simulations of Water Adsorption in Confined Media

et al. 2014

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“…The theory has been used previously to model pure water at hydrophobic surfaces and was found to predict the structure and properties of water around hydrophobic solutes well. 46 Mixtures of water with different polar and nonpolar molecules have been modeled in both the bulk and at an interface using a SAFT based approach. [47][48][49][50] Section II describes the model used for the alcohol and water and the theory used to obtain the structure and thermodynamic properties.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobic and hydrophilic interactions in aqueous mixtures of alcohols at a hydrophobic surface

Ballal

Chapman

2013

The Journal of Chemical Physics

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Aqueous solutions of alcohols are interesting because of their anomalous behavior that is believed to be due to the molecular structuring of water and alcohol around each other in solution. The interfacial structuring and properties are significant for application in alcohol purification processes and biomolecular structure. Here we study aqueous mixtures of short alcohols (methanol, ethanol, 1-propanol, and 2-propanol) at a hydrophobic surface using interfacial statistical associating fluid theory which is a perturbation density functional theory. The addition of a small amount of alcohol decreases the interfacial tension of water drastically. This trend in interfacial tension can be explained by the structure of water and alcohol next to the surface. The hydrophobic group of an added alcohol preferentially goes to the surface preserving the structure of water in the bulk. For a given bulk alcohol concentration, water mixed with the different alcohols has different interfacial tensions with propanol having a lower interfacial tension than methanol and ethanol. 2-propanol is not as effective in decreasing the interfacial tension as 1-propanol because it partitions poorly to the surface due to its larger excluded volume. But for a given surface alcohol mole fraction, all the alcohol mixtures give similar values for interfacial tension. For separation of alcohol from water, methods that take advantage of the high surface mole fraction of alcohol have advantages compared to separation using the vapor in equilibrium with a water-alcohol liquid. © 2013 AIP Publishing LLC.

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“…As there are too many for us to cite all, we mention several that we find significant and we concentrate on the more recent literature. The studies include ab initio MO theory,[21–23] empirical[24,25] and first principles[26,27] molecular dynamics[28–30] and other approaches. [31–37] A review of the hydrophobic effect on large systems has been recently published.…”

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confidence: 99%

A density functional theory evaluation of hydrophobic solvation: Ne, Ar and Kr in a 50-water cluster – Implications for the hydrophobic effect

Kobko

Marianski

Asensio

et al. 2012

Computational and Theoretical Chemistry

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The physical explanation for the hydrophobic effect has been the subject of disagreement. Physical organic chemists tend to use a explanation related to pressure, while many biochemists prefer an explanation that involves decreased entropy of the aqueous solvent. We present DFT calculations at the B3LYP/6-31G(d,p) and X3LYP/6-31G(d,p) levels on the solvation of three noble gases (Ne, Ar, and Kr) in clusters of 50 waters. Vibrational analyses show no substantial decreases in the vibrational entropies of the waters in any of the three clusters. The observed positive free energies of transfer from the gas phase or from nonpolar solvents to water appear to be due to the work needed to make a suitable hole in the aqueous solvent. We distinguish between hydrophobic solvations (explicitly studied here) and the hydrophobic effect that occurs when a solute (or transition state) can decrease its volume through conformational change (which is not possible for the noble gases).

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Hydration Structure and Interfacial Properties of Water near a Hydrophobic Solute from a Fundamental Measure Density Functional Theory

Cited by 18 publications

References 76 publications

Nonlocal Density Functional Theory and Grand Canonical Monte Carlo Molecular Simulations of Water Adsorption in Confined Media

Nonlocal Density Functional Theory and Grand Canonical Monte Carlo Molecular Simulations of Water Adsorption in Confined Media

Hydrophobic and hydrophilic interactions in aqueous mixtures of alcohols at a hydrophobic surface

A density functional theory evaluation of hydrophobic solvation: Ne, Ar and Kr in a 50-water cluster – Implications for the hydrophobic effect

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