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Title: Molecular Theory of Hydration at Different Temperatures

Abstract

Solvation plays an important role in diverse chemical processes ranging from reaction kinetics to molecular recognition, solubility, and phase separations. Despite a long-history of theoretical exploration, quantitative prediction of solvation remains a theoretical challenge without relying on the macroscopic properties of the solvent as an input. Here we present a molecular density functional theory that provides a self-consistent description of the solvation structure and thermodynamic properties of small organic molecules in liquid water at different temperatures. Based on the solute configuration and force-field parameters generated from first-principles calculations, the theoretical predictions are found in good agreement with experimental data for the hydration free energies of 197 organic molecules in a temperature range from 0 to 40 °C. In addition to calibration with experimental results, the theoretical predictions are compared with recent molecular dynamics simulations for the hydration of five highly explosive nitrotoluenes. Lastly, this work demonstrates the potential of the classical density functional theory for high-throughput prediction of solvation properties over a broad range of temperatures.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Univ. of California, Riverside, CA (United States). Dept. of Chemical and Environmental Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1480286
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 28; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Sheng, Shijie, Miller, Michael, and Wu, Jianzhong. Molecular Theory of Hydration at Different Temperatures. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b04264.
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Sheng, Shijie, Miller, Michael, & Wu, Jianzhong. Molecular Theory of Hydration at Different Temperatures. United States. https://doi.org/10.1021/acs.jpcb.7b04264
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Sheng, Shijie, Miller, Michael, and Wu, Jianzhong. Thu . "Molecular Theory of Hydration at Different Temperatures". United States. https://doi.org/10.1021/acs.jpcb.7b04264. https://www.osti.gov/servlets/purl/1480286.
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@article{osti_1480286,
title = {Molecular Theory of Hydration at Different Temperatures},
author = {Sheng, Shijie and Miller, Michael and Wu, Jianzhong},
abstractNote = {Solvation plays an important role in diverse chemical processes ranging from reaction kinetics to molecular recognition, solubility, and phase separations. Despite a long-history of theoretical exploration, quantitative prediction of solvation remains a theoretical challenge without relying on the macroscopic properties of the solvent as an input. Here we present a molecular density functional theory that provides a self-consistent description of the solvation structure and thermodynamic properties of small organic molecules in liquid water at different temperatures. Based on the solute configuration and force-field parameters generated from first-principles calculations, the theoretical predictions are found in good agreement with experimental data for the hydration free energies of 197 organic molecules in a temperature range from 0 to 40 °C. In addition to calibration with experimental results, the theoretical predictions are compared with recent molecular dynamics simulations for the hydration of five highly explosive nitrotoluenes. Lastly, this work demonstrates the potential of the classical density functional theory for high-throughput prediction of solvation properties over a broad range of temperatures.},
doi = {10.1021/acs.jpcb.7b04264},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 28,
volume = 121,
place = {United States},
year = {Thu Jun 22 00:00:00 EDT 2017},
month = {Thu Jun 22 00:00:00 EDT 2017}
}
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https://doi.org/10.1021/acs.jpcb.7b04264
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