Molecular Theory of Hydration at Different Temperatures

doi:10.1021/acs.jpcb.7b04264

Title: Molecular Theory of Hydration at Different Temperatures

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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:

Sheng, Shijie ^[1]; Miller, Michael ^[1];

^[1]

Univ. of California, Riverside, CA (United States). Dept. of Chemical and Environmental Engineering

Publication Date:: 2017-06-22

Research Org.:: Lawrence Berkeley National Lab. (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

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.  doi: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.  doi: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         = {2017},

  month        = {6}

}

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DOI: 10.1021/acs.jpcb.7b04264

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