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

Chaudhari, Mangesh I.; Rempe, Susan B.; Asthagiri, D.; Tan, L.; Pratt, L. R.

doi:10.1021/acs.jpcb.5b09552

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

Journal Article · Tue Dec 22 04:00:00 UTC 2015 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI: https://doi.org/10.1021/acs.jpcb.5b09552 · OSTI ID:1237355

Chaudhari, Mangesh I. ^[1]; Rempe, Susan B. ^[1]; Asthagiri, D. ^[2]; Tan, L. ^[3]; Pratt, L. R. ^[3]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Material Sciences
Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering

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.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; Consortium for Ocean Leadership (United States)

Contributing Organization:: Tulane Univ., New Orleans, LA (United States); Rice Univ., Houston, TX (United States)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1237355

Report Number(s):: SAND--2015-20729J; 555995

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 8 Vol. 120; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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