Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects

The Journal of Physical Chemistry. B
Ang GaoJohn D Weeks

Abstract

The role that van der Waals (vdW) attractive forces play in the hydration and association of atomic hydrophobic solutes such as argon (Ar) in water is reanalyzed using the local molecular field (LMF) theory of those interactions. In this problem, solute vdW attractive forces can reduce or mask hydrophobic interactions as measured by contact peak heights of the ArAr correlation function compared to reference results for purely repulsive core solutes. Nevertheless, both systems exhibit a characteristic hydrophobic inverse temperature behavior in which hydrophobic association becomes stronger with increasing temperature through a moderate temperature range. The new theoretical approximation obtained here is remarkably simple and faithful to the statistical mechanical LMF assessment of the necessary force balance. Our results extend and significantly revise approximations made in a recent application of the LMF approach to this problem and, unexpectedly, support a theory of nearly 40 years ago.

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Citations

Jan 9, 2020·Proceedings of the National Academy of Sciences of the United States of America·Ang GaoJohn D Weeks
Aug 5, 2020·Proceedings of the National Academy of Sciences of the United States of America·Stephen J Cox
May 16, 2020·Physical Chemistry Chemical Physics : PCCP·Aria J Bredt, Dor Ben-Amotz
Jul 20, 2021·Chemical Science·Sara GómezAlbeiro Restrepo
Jul 28, 2021·The Journal of Physical Chemistry. B·Dilipkumar N AsthagiriLawrence R Pratt
Nov 11, 2020·The Journal of Physical Chemistry Letters·Dheeraj S TomarDilipkumar N Asthagiri
May 24, 2019·Journal of the American Chemical Society·Dor Ben-Amotz
Jan 27, 2019·The Journal of Physical Chemistry. B·Zhitong JiangAmish J Patel

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