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Journal of Chemical Physics / Volume 136 / Issue 4 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 136, 044511 (2012); http://dx.doi.org/10.1063/1.3677185 (10 pages)

Modeling simple amphiphilic solutes in a Jagla solvent

Zhiqiang Su1, Sergey V. Buldyrev1,2, Pablo G. Debenedetti3, Peter J. Rossky4, and H. Eugene Stanley1

1Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215, USA
2Department of Physics, Yeshiva University, 500 West 185th Street, New York, New York 10033, USA
3Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA
4Department of Chemistry and Biochemistry, College of Natural Science, The University of Texas at Austin, Austin, Texas 78712, USA

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(Received 7 September 2011; accepted 24 December 2011; published online 25 January 2012)

Methanol is an amphiphilic solute whose aqueous solutions exhibit distinctive physical properties. The volume change upon mixing, for example, is negative across the entire composition range, indicating strong association. We explore the corresponding behavior of a Jagla solvent, which has been previously shown to exhibit many of the anomalous properties of water. We consider two models of an amphiphilic solute: (i) a “dimer” model, which consists of one hydrophobic hard sphere linked to a Jagla particle with a permanent bond, and (ii) a “monomer” model, which is a limiting case of the dimer, formed by concentrically overlapping a hard sphere and a Jagla particle. Using discrete molecular dynamics, we calculate the thermodynamic properties of the resulting solutions. We systematically vary the set of parameters of the dimer and monomer models and find that one can readily reproduce the experimental behavior of the excess volume of the methanol-water system as a function of methanol volume fraction. We compare the pressure and temperature dependence of the excess volume and the excess enthalpy of both models with experimental data on methanol-water solutions and find qualitative agreement in most cases. We also investigate the solute effect on the temperature of maximum density and find that the effect of concentration is orders of magnitude stronger than measured experimentally.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. MODEL AND METHODS
    1. Dimer model for amphiphilic solutes
    2. Monomer model for amphiphilic solutes
    3. Simulation details and analysis methods
  3. RESULTS AND DISCUSSION
    1. Effects of the parameters on model behavior
    2. Temperature and pressure dependence of the excess volume
    3. Excess enthalpy
    4. Effect on the temperature of maximum density
  4. CONCLUSION

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KEYWORDS and PACS

Keywords

bonds (chemical), enthalpy, hydrophobicity, molecular dynamics method, organic compounds, solvent effects

PACS

  • 61.20.Ja

    Computer simulation of liquid structure

  • 31.15.xv

    Molecular dynamics and other numerical methods

  • 65.20.Jk

    Studies of thermodynamic properties of specific liquids

  • 33.15.Fm

    Bond strengths, dissociation energies

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3677185

PUBLICATION DATA

ISSN

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

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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