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

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. In conclusion, 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.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Maryland, College Park, MD (United States). Inst. for Physical Science and Technology, and Dept. of Chemistry and Biochemistry
  2. Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Engineering Sciences
  4. Rice Univ., Houston, TX (United States). Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1474051
Report Number(s):
[SAND-2018-10155J]
[Journal ID: ISSN 1520-6106; 667918]
Grant/Contract Number:  
[AC04-94AL85000]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
[ Journal Volume: 122; Journal Issue: 23]; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gao, Ang, Tan, Liang, Chaudhari, Mangesh I., Asthagiri, D., Pratt, Lawrence R., Rempe, Susan B., and Weeks, John D. Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects. United States: N. p., 2018. Web. doi:10.1021/acs.jpcb.8b01711.
Gao, Ang, Tan, Liang, Chaudhari, Mangesh I., Asthagiri, D., Pratt, Lawrence R., Rempe, Susan B., & Weeks, John D. Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects. United States. doi:10.1021/acs.jpcb.8b01711.
Gao, Ang, Tan, Liang, Chaudhari, Mangesh I., Asthagiri, D., Pratt, Lawrence R., Rempe, Susan B., and Weeks, John D. Wed . "Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects". United States. doi:10.1021/acs.jpcb.8b01711. https://www.osti.gov/servlets/purl/1474051.
@article{osti_1474051,
title = {Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects},
author = {Gao, Ang and Tan, Liang and Chaudhari, Mangesh I. and Asthagiri, D. and Pratt, Lawrence R. and Rempe, Susan B. and Weeks, John D.},
abstractNote = {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. In conclusion, 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.},
doi = {10.1021/acs.jpcb.8b01711},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = [23],
volume = [122],
place = {United States},
year = {2018},
month = {5}
}

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Figures / Tables:

FIG. 1 FIG. 1: Radial distribution function of argon atoms (A) modeled as Lennard-Jones spheres in SPC/E water. Note the strong hydrophobic contact attraction, together with the clear inverse temperature behavior. The 97% confidence intervals for the T = 300K results, evaluated with GROMACS weighted-histogram (WHAM) bootstrap tools23, are smaller than themore » plotting symbols. The inset shows the radial distribution function of repulsive core A0 atoms, again showing strong inverse temperature behavior but with notably higher first peak heights. See Methods section below for procedural details.« less

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