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Title: Molecular theory and the effects of solute attractive forces on hydrophobic interactions

Abstract

The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. In this paper, we present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar–Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are opposite in sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasichemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar–Ar rdfs permit evaluation of osmotic second virial coefficients B2. Those B2’s also show that incorporation of attractive interactions leads to more positivemore » (repulsive) values. With attractive interactions in play, B2 can change from positive to negative values with increasing temperatures. Furthermore, this is consistent with the puzzling suggestions of decades ago that B2 ≈ 0 for intermediate cases of temperature or solute size. In all cases here, B2 becomes more attractive with increasing temperature.« less

Authors:
 [1];  [1];  [2];  [3];  [3]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Material Sciences
  2. Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
  3. Tulane Univ., New Orleans, LA (United States). Dept. of 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); USDOE Laboratory Directed Research and Development (LDRD) Program; Consortium for Ocean Leadership (United States)
Contributing Org.:
Tulane Univ., New Orleans, LA (United States); Rice Univ., Houston, TX (United States)
OSTI Identifier:
1237355
Alternate Identifier(s):
OSTI ID: 1347346
Report Number(s):
SAND-2015-20729J; SAND2015-1893J
Journal ID: ISSN 1520-6106; 555995; TRN: US1600392
Grant/Contract Number:  
AC04-94AL85000; SA 12-05/GoMRI-002
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 120; Journal Issue: 8; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Chaudhari, Mangesh I., Rempe, Susan B., Asthagiri, D., Tan, L., and Pratt, L. R. Molecular theory and the effects of solute attractive forces on hydrophobic interactions. United States: N. p., 2015. Web. doi:10.1021/acs.jpcb.5b09552.
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Chaudhari, Mangesh I., Rempe, Susan B., Asthagiri, D., Tan, L., & Pratt, L. R. Molecular theory and the effects of solute attractive forces on hydrophobic interactions. United States. https://doi.org/10.1021/acs.jpcb.5b09552
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Chaudhari, Mangesh I., Rempe, Susan B., Asthagiri, D., Tan, L., and Pratt, L. R. Tue . "Molecular theory and the effects of solute attractive forces on hydrophobic interactions". United States. https://doi.org/10.1021/acs.jpcb.5b09552. https://www.osti.gov/servlets/purl/1237355.
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@article{osti_1237355,
title = {Molecular theory and the effects of solute attractive forces on hydrophobic interactions},
author = {Chaudhari, Mangesh I. and Rempe, Susan B. and Asthagiri, D. and Tan, L. and Pratt, L. R.},
abstractNote = {The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. In this paper, we present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar–Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are opposite in sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasichemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar–Ar rdfs permit evaluation of osmotic second virial coefficients B2. Those B2’s also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, B2 can change from positive to negative values with increasing temperatures. Furthermore, this is consistent with the puzzling suggestions of decades ago that B2 ≈ 0 for intermediate cases of temperature or solute size. In all cases here, B2 becomes more attractive with increasing temperature.},
doi = {10.1021/acs.jpcb.5b09552},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 8,
volume = 120,
place = {United States},
year = {Tue Dec 22 00:00:00 EST 2015},
month = {Tue Dec 22 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acs.jpcb.5b09552
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