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Hydrophobic force, a Casimir-like effect due to hydrogen-bond fluctuations

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  • Kanth, Jampa Maruthi Pradeep
  • Anishetty, Ramesh

Abstract

Hydrophobic force, interfacial tension, and transverse density profile in a confined water system are addressed from first principles of statistical mechanics in a lattice model for water. Using the molecular mean field theory technique we deduce explicit expressions for each of the above mentioned phenomena and show that hydrophobic force is a manifestation of a Casimir-like effect due to hydrogen-bond fluctuations in confined water. It is largely influenced by the long range correlations of orientational fluctuations. Furthermore, the temperature dependence of hydrophobic force between large non-polar surfaces is suggested to be different from that between small solutes. The mechanisms contributing to characteristic behavior in each case are identified. In the case of large surfaces, the prevalence of discrete fluctuation modes in the confinement direction and their entropic contribution to the overall free energy dominate the temperature dependence. Mode discretization is also implicated in the variation of interfacial tension with separation distance between confining surfaces and characteristic density profile of the confined fluid. All the computations are parameter free and compare favorably with results of molecular dynamics simulations and experiments.

Suggested Citation

  • Kanth, Jampa Maruthi Pradeep & Anishetty, Ramesh, 2013. "Hydrophobic force, a Casimir-like effect due to hydrogen-bond fluctuations," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 392(20), pages 4804-4823.
    • Handle: RePEc:eee:phsmap:v:392:y:2013:i:20:p:4804-4823
    DOI: 10.1016/j.physa.2013.06.036
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    References listed on IDEAS

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    1. C. Hertlein & L. Helden & A. Gambassi & S. Dietrich & C. Bechinger, 2008. "Direct measurement of critical Casimir forces," Nature, Nature, vol. 451(7175), pages 172-175, January.
    2. Yuen-Kit Cheng & Peter J. Rossky, 1998. "Surface topography dependence of biomolecular hydrophobic hydration," Nature, Nature, vol. 392(6677), pages 696-699, April.
    3. Kanth, Jampa Maruthi Pradeep & Anishetty, Ramesh, 2012. "Molecular mean field theory for liquid water," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 391(3), pages 439-455.
    4. David Chandler, 2005. "Interfaces and the driving force of hydrophobic assembly," Nature, Nature, vol. 437(7059), pages 640-647, September.
    5. Attard, Phil & Moody, Michael P. & Tyrrell, James W.G., 2002. "Nanobubbles: the big picture," Physica A: Statistical Mechanics and its Applications, Elsevier, vol. 314(1), pages 696-705.
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